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Sample records for cationic gold clusters

  1. Carbon monoxide adsorption on neutral and cationic vanadium doped gold clusters

    OpenAIRE

    Le, Hai Thuy; Lang, Sandra M; de Haeck, Jorg; Lievens, Peter; Janssens, Ewald

    2012-01-01

    The effect of a single vanadium dopant atom on the reactivity of small gold clusters is studied in the gas phase. In particular we investigated carbon monoxide adsorption on vanadium doped gold clusters using a low-pressure collision cell. Employing this technique the reactivity of both neutral and cationic clusters was studied under the same experimental conditions. Analysis of the kinetic data as a function of the pressure in the reaction cell shows that the reaction mechanism is composed o...

  2. Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-11-29

    The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2. Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state

  3. Cluster self-assembly of di[gold(I)]halonium cations

    OpenAIRE

    Schmidbaur, Hubert; Hamel, Armin; Mitzel, Norbert W.; Schier, Annette; Nogai, Stefan

    2002-01-01

    Treatment of gold(I) halide complexes of the type L-Au-X [where L = PPh3, PEt3 with X = Cl, Br, I, or L = 2,6-(MeO)2C6H3PPh2 with X = Cl] with AgSbF6 in the molar ratio 2:1 in dichloromethane/tetrahydrofuran at −78°C affords high yields of di[gold(I)]halonium salts of the formula {X[Au(PR3)]2}+ SbF\\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrs...

  4. 2D-3D Transition for Cationic and Anionic Gold Clusters: A Kinetic Energy Density Functional Study

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Hammer, Bjørk; Madsen, Georg

    2009-01-01

    We present a density functional theory study of the energetics of isolated Aun+ (n = 5-10) and Aun- (n = 8-13) gold clusters. We compare our results to both theoretical and experimental values from the literature and find the use of meta-generalized gradient approximation (MGGA) functionals, in...

  5. The interaction of gold and silver nanoparticles with a range of anionic and cationic dyes

    OpenAIRE

    Kitching, H; Kenyon, A. J.; Parkin, I. P.

    2014-01-01

    We describe the synthesis of charge-stabilised gold and silver nanoparticles by a modified Turkevich method and their interaction with a selection of cationic and anionic dyes. It was found that gold nanoparticles interact strongly with cationic dyes and in some cases enhanced absorption was observed by UV-visible spectroscopy. It is also shown that addition of cationic dyes to gold nanoparticles triggers aggregation of the nanoparticles into large, micrometre-scale clusters. Simultaneous fra...

  6. Size-dependent stability toward dissociation and ligand binding energies of phosphine-ligated gold cluster ions

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2014-01-01

    The stability of sub-nanometer size gold clusters ligated with organic molecules is of paramount importance to the scalable synthesis of monodisperse size-selected metal clusters with highly tunable chemical and physical properties. For the first time, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS) equipped with surface induced dissociation (SID) has been employed to investigate the time and collision energy resolved fragmentation behavior of cationic doubly charged gold clusters containing 7-9 gold atoms and 6-7 triphenylphosphine (TPP) ligands prepared by reduction synthesis in solution. The TPP ligated gold clusters are demonstrated to fragment through three primary dissociation pathways: (1) Loss of a neutral TPP ligand from the precursor gold cluster, (2) asymmetric fission and (3) symmetric fission and charge separation of the gold core resulting in formation of complementary pairs of singly charged fragment ions. Threshold energies and activation entropies of these fragmentation pathways have been determined employing Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental SID data. It is demonstrated that the doubly charged cluster ion containing eight gold atoms and six TPP ligands, (8,6)2+, exhibits exceptional stability compared to the other cationic gold clusters examined in this study due to its large ligand binding energy of 1.76 eV. Our findings demonstrate the dramatic effect of the size and extent of ligation on the gas-phase stability and preferred fragmentation pathways of small TPP-ligated gold clusters.

  7. Strengthening gold-gold bonds by complexing gold clusters with noble gases

    OpenAIRE

    Ghiringhelli, Luca M.; Levchenko, Sergey V.

    2015-01-01

    We report an unexpectedly strong and complex chemical bonding of rare-gas atoms to neutral gold clusters. The bonding features are consistently reproduced at different levels of approximation within density-functional theory and beyond: from GGA, through hybrid and double-hybrid functionals, up to renormalized second-order perturbation theory. The main finding is that the adsorption of Ar, Kr, and Xe reduces electron-electron repulsion within gold dimer, causing strengthening of the Au-Au bon...

  8. Blackbody-induced radiative dissociation of cationic SF 6 clusters

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahinov, I.; Schwalm, D.;

    2012-01-01

    The stability of cationic SF5+(SF6)n−1 clusters was investigated by measuring their blackbody-induced radiative dissociation (BIRD) rates. The clusters were produced in a supersonic expansion ion source and stored in an electrostatic ion-beam trap at room temperature, where their abundances and...... lifetimes were measured. Using the “master equation” approach, relative binding energies of an SF6 unit in the clusters could be extracted from the storage-time dependence of the survival probabilities. The results allow for a deeper insight into the effect of a localized charge on the structure and...... stability of SF6-based clusters....

  9. Structure, spectra and dynamics of alkali cation microhydration clusters

    OpenAIRE

    Schulz, Franziska

    2005-01-01

    The main focus of this work was the theoretical investigation of alkali cation microhydration clusters with sodium, potassium, and caesium as central ion and up to 24 water molecules per cluster. Structures were obtained applying global geometry optimisation, using a specialised version of genetic algorithms and the common TIP4P/OPLS model potential. The global and most important local minimum energy structures have been investigated and the results obtained constitute a first complete and sy...

  10. GOLD CLUSTER LABELS AND RELATED TECHNOLOGIES IN MOLECULAR MORPHOLOGY.

    Energy Technology Data Exchange (ETDEWEB)

    HAINFELD,J.F.; POWELL,R.D.

    2004-02-04

    Although intensely colored, even the largest colloidal gold particles are not, on their own, sufficiently colored for routine use as a light microscopy stain: only with very abundant antigens or with specialized illumination methods can bound gold be seen. Colloidal gold probes were developed primarily as markers for electron microscopy, for which their very high electron density and selectivity for narrow size distributions when prepared in different ways rendered them highly suited. The widespread use of gold labeling for light microscopy was made possible by the introduction of autometallographic enhancement methods. In these processes, the bound gold particles are exposed to a solution containing metal ions and a reducing agent; they catalyze the reduction of the ions, resulting in the deposition of additional metal selectively onto the particles. On the molecular level, the gold particles are enlarged up to 30-100 nm in diameter; on the macroscale level, this results in the formation of a dark stain in regions containing bound gold particles, greatly increasing visibility and contrast. The applications of colloidal gold have been described elsewhere in this chapter, we will focus on the use of covalently linked cluster complexes of gold and other metals. A gold cluster complex is a discrete molecular coordination compound comprising a central core, or ''cluster'' of electron-dense metal atoms, ligated by a shell of small organic molecules (ligands), which are linked to the metal atoms on the surface of the core. This structure gives clusters several important advantages as labels. The capping of the metal surface by ligands prevents non-specific binding to cell and tissue components, which can occur with colloidal gold. Cluster compounds are more stable and may be used under a wider range of conditions. Unlike colloidal gold, clusters do not require additional macromolecules such as bovine serum albumin or polyethylene glycol for

  11. A theoretical study on interaction of proline with gold cluster

    Indian Academy of Sciences (India)

    Sandhya Rai; N V Suresh Kumar; Harjinder Singh

    2012-06-01

    Interaction of proline with gold cluster was studied using density functional theory (DFT). Two types of mixed basis sets UB3LYP/6-311++G ∪ LANL2MB and UB3LYP/6-311++G ∪ LANL2DZ were used for optimization of complex structures. Proline interacts with gold cluster either through one anchor bond, N–Au or an anchor bond O–Au associated with a non-conventional O–H…Au hydrogen bond. Among these interactions, higher tendency for interaction is seen with Au cluster through amide terminal. Natural bond orbital analysis (NBO) is used to substantiate the results.

  12. Fluorescent Thiol-Derivatized Gold Clusters Embedded in Polymers

    Directory of Open Access Journals (Sweden)

    G. Carotenuto

    2013-01-01

    Full Text Available Owing to aurophilic interactions, linear and/or planar Au(I-thiolate molecules spontaneously aggregate, leading to molecular gold clusters passivated by a thiolate monolayer coating. Differently from the thiolate precursors, such cluster compounds show very intensive visible fluorescence characteristics that can be tuned by alloying the gold clusters with silver atoms or by conjugating the electronic structure of the metallic core with unsaturated electronic structures in the organic ligand through the sulphur atom. Here, the photoluminescence features of some examples of these systems are shortly described.

  13. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  14. Structures of 38-atom gold-platinum nanoalloy clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.

  15. Structures of 38-atom gold-platinum nanoalloy clusters

    International Nuclear Information System (INIS)

    Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, AunPt38−n (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature

  16. Geometry, chemical reactivity and Raman spectra of gold clusters

    Directory of Open Access Journals (Sweden)

    Ngangbam Bedamani Singh

    2015-12-01

    Full Text Available Structures, stability, and chemical reactivity of Aun (n = 2-10 clusters are investigated using density functional theory (DFT. We have studied the reactivity parameters of the clusters in terms of relevant electronic structure principles. It is observed that stability and properties are strongly dependent on the cluster size. Clusters with an even number of atoms are found to be energetically and chemically more stable than odd-numbered clusters. Electronic structure of clusters has been investigated using partial density of states (PDOS. PDOS analysis clearly shows that energy states of highest occupied molecular orbital and lowest unoccupied molecular orbital are predominantly contributed by s orbital. From time-dependent DFT calculations, it is shown that absorption spectra of even-numbered clusters are more intense and are observed at lower wavelength region than the odd-sized gold clusters.

  17. Understanding ligand effects in gold clusters using mass spectrometry.

    Science.gov (United States)

    Johnson, Grant E; Laskin, Julia

    2016-06-21

    This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because "each-atom-counts" toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation of numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom

  18. Highly stable noble metal nanoparticles dispersible in biocompatible solvents: synthesis of cationic phosphonium gold nanoparticles in water and DMSO.

    Science.gov (United States)

    Ju-Nam, Yon; Abdussalam-Mohammed, Wanisa; Ojeda, Jesus J

    2016-04-12

    In this work, we report the synthesis of novel cationic phosphonium gold nanoparticles dispersible in water and dimethyl sulfoxide (DMSO) for their potential use in biomedical applications. All the cationic-functionalising ligands currently reported in the literature are ammonium-based species. Here, the synthesis and characterisation of an alternative system, based on phosphonioalkylthiosulfate zwitterions and phosphonioalkylthioacetate were carried out. We have also demonstrated that our phosphonioalkylthiosulfate zwitterions readily disproportionate into phosphonioalkylthiolates in situ during the synthesis of gold nanoparticles produced by the borohydride reduction of gold(iii) salts. The synthesis of the cationic gold nanoparticles using these phosphonium ligands was carried out in water and DMSO. UV-visible spectroscopic and TEM studies have shown that the phosphonioalkylthiolates bind to the surface of gold nanoparticles which are typically around 10 nm in diameter. The resulting cationic-functionalised gold nanoparticles are dispersible in aqueous media and in DMSO, which is the only organic solvent approved by the U.S. Food and Drug Administration (FDA) for drug carrier tests. This indicates their potential future use in biological applications. This work shows the synthesis of a new family of phosphonium-based ligands, which behave as cationic masked thiolate ligands in the functionalisation of gold nanoparticles. These highly stable colloidal cationic phosphonium gold nanoparticles dispersed in water and DMSO can offer a great opportunity for the design of novel biorecognition and drug delivery systems. PMID:26796782

  19. Ligand-protected gold clusters: the structure, synthesis and applications

    Science.gov (United States)

    Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

    2015-11-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

  20. Synthesis and characterization of gold nanoparticles - cationic polythiophene nanocomposites for optoelectronics applications

    Czech Academy of Sciences Publication Activity Database

    Kazim, Samrana; Pfleger, Jiří; Vohlídal, J.; Bondarev, D.

    Badajoz : Formatex Research Center, 2012. s. 342. [The Energy & Materials Research Conference - EMR 2012. 20.06.2012-22.06.2012, Torremolinos] R&D Projects: GA ČR GAP208/10/0941; GA MŠk 7E10040 EU Projects: European Commission(XE) 247745 - FlexNet Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : cationic polythiophene * gold nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry

  1. Clustering effects on discontinuous gold film NanoCells.

    Science.gov (United States)

    Seminario, Jorge M; Ma, Yuefei; Agapito, Luis A; Yan, Liuming; Araujo, Roy A; Bingi, Sridhar; Vadlamani, Nagendra S; Chagarlamudi, Krishna; Sudarshan, Tangali S; Myrick, Michael L; Colavita, Paula E; Franzon, Paul D; Nackashi, David P; Cheng, Long; Yao, Yuxing; Tour, James M

    2004-09-01

    Reproducible negative differential resistance (NDR)-like switching behavior is observed in NanoCells. This behavior is attributed to the formation of filaments and clusters between the discontinuous gold films. Control experiments are performed by self-assembly of insulating molecules between the gold islands and conducting molecules on these islands. Additional control experiments are performed by removing the filaments and clusters between islands using a piranha bath. The results are consistent with theoretical predictions and extend the domain of molecular electronics based in organic molecules to include nanosized clusters as active units. This facilitates a scenario where synthetically accessible organic molecules, with defined characteristics, can be adjusted by metallic nanoclusters as an in situ fine-tuning element, able to compensate for the lack of addressing in the nanosize regime. PMID:15570981

  2. Cage Clusters of Gold and Tin: Golden Buckyballs and Stannaspherene

    Science.gov (United States)

    Wang, Lai-Sheng

    2008-03-01

    Photoelectron spectroscopy (PES) yields direct electronic structure information for size-selected clusters. Combining PES with theoretical calculations has become an effective approach to obtain structural information for small and medium-sized clusters. We present recent discoveries of two classes of cage clusters in gold and tin. Negatively charged gold clusters (Aun^-) have been shown to exhibit a remarkable structural diversity from 2D structures for n = 4-12 and the pyramidal structure for n = 20. Using PES and DFT calculations, we have found that gold clusters with n = 16-18 possess unprecedented hollow cage structures. We have been able to successfully dope a variety of transition-metal atoms into the empty spaces in the golden cages, confirming their structural robustness, as well as demonstrating chemical tuning of their electronic, magnetic, and catalytic properties. Unlike carbon, the heavier congeners of the group 14 elements are not known to form hollow cage structures similar to the fullerenes. In PES studies of tin clusters, we noted that the spectrum of Sn12^- is distinctly different from that of its neighbors or its Si/Ge counterpart. This observation led to our discovery of a highly symmetric and stable icosahedral Sn12^2- cage, for which we coined a name ``stannaspherene'' to describe its high symmetry and spherical pi bonding. We have also shown that all transition metals including the f-block elements can be doped inside Sn12^2- to form a whole class of endohedral stannaspherenes, which may be used as potential building blocks for new cluster-assembled materials. In a preliminary experiment to synthesize stannaspherene in the bulk, a new cluster, Pd2@Sn18^4-, was crystallized and characterized, suggesting all stannaspherene and endohedral stannasphernes may be fabricated in the bulk under suitable conditions.

  3. Change Color Effect and Spectral Properties of Gold Nanoparticle-cationic Surfactants System

    Institute of Scientific and Technical Information of China (English)

    JIANG Zhi-liang; PAN Hong-cheng; YUAN Wei-en

    2004-01-01

    The change color effect of gold nanoparticle solutions was studied by means of resonance scattering and absorption spectrometry and scan electron microscopy. The red Au nanoparticles with a size of 10 nm exhibit a resonance absorption peak and a resonance scattering peak all at 525 nm. After some inorganic electrolyte was added to a red Au nanoparticles solution, the color of the solution became blue and the absorbance at 600-700 nm was significantly increased. The ratio of the concentration of monovalent cations, at which the resonance scattering of the system at 525 nm is maximal to that of divalent cations, is in the range of 100 : 1 -100 : 1.8. It is in good agreement with the Schulze-Hardy rule of the coagulation value of electrolyte. After adding some cationic surfactants to the above solution, the color of the solution is in deep blue, with two resonance absorption peaks at 550 and 680 nm, and a greatly enhanced resonance scattering peak at 525 nm.The experiments demonstrate that the stronger the hydrophobicity of the cationic surfactant is, the stronger the change color effect of the Au nanoparticle solution promoted by cationic surfactant is. The change color effect of Au nanoparticle solution is resulted from the increased diameter of Au nanoparticles, and the changes of resonance absorption peak and resonance scattering.

  4. The different roles of a cationic gold(i) complex in catalysing hydroarylation of alkynes and alkenes with a heterocycle.

    Science.gov (United States)

    Mehrabi, Tahmineh; Ariafard, Alireza

    2016-08-01

    The mechanism of twofold hydroarylation of terminal alkynes with pyrrole catalyzed by a cationic gold(i) complex was investigated using DFT. It was found that while both the hydroarylation reactions proceed via a Friedel-Crafts-type mechanism, the first hydroarylation is directly promoted by gold(i) but the second hydroarylation by a proton released through interaction of the alkene product with gold-bound acidic organic species such as acetic acid and terminal alkynes. PMID:27377712

  5. Mammographic calcification cluster detection and threshold gold thickness measurements

    Science.gov (United States)

    Warren, L. M.; Mackenzie, A.; Cooke, J.; Given-Wilson, R.; Wallis, M. G.; Chakraborty, D. P.; Dance, D. R.; Young, K. C.

    2012-03-01

    European Guidelines for quality control in digital mammography specify acceptable and achievable standards of image quality (IQ) in terms of threshold gold thickness using the CDMAM test object. However, there is little evidence relating such measurements to cancer detection. This work investigated the relationship between calcification detection and threshold gold thickness. An observer study was performed using a set of 162 amorphous selenium direct digital (DR) detector images (81 no cancer and 81 with 1-3 inserted calcification clusters). From these images four additional IQs were simulated: different digital detectors (computed radiography (CR) and DR) and dose levels. Seven observers marked and rated the locations of suspicious regions. DBM analysis of variances was performed on the JAFROC figure of merit (FoM) yielding 95% confidence intervals for IQ pairs. Automated threshold gold thickness (Tg) analysis was performed for the 0.25mm gold disc diameter on CDMAM images at the same IQs (16 images per IQ). Tg was plotted against FoM and a power law fitted to the data. There was a significant reduction in FoM for calcification detection for CR images compared with DR; FoM decreased from 0.83 to 0.63 (pIQ. Since the majority of threshold gold thicknesses for the various IQs were above the acceptable standard despite large variations in calcification detection by radiologists, current EU guidelines may need revising.

  6. The structure and morphology of gold nanoparticles produced in cationic gemini surfactant systems

    Science.gov (United States)

    Murawska, Magdalena; Wiatr, Michalina; Nowakowski, Paweł; Szutkowski, Kosma; Skrzypczak, Andrzej; Kozak, Maciej

    2013-12-01

    Potential applications of gold nanoparticles (GNP) are strictly connected with their size and shape. The influence of different dicationic (gemini) surfactants, alkyloxymethylimidazolium derivatives derivatives, on the structure and morphology of GNP was studied. The synthesis of nanoparticles was performed in the presence of various gemini surfactants—dodecyloxymethylimidazolium nitrate (IMI_NO3_C4_C12), propionate (IMI_PROP_C4_C12) and 3,3'-[1,9-(2,8-dioxanonane)]bis-(1-nonyloxymethylimidazolium) chloride (IMI_Cl_oxyC7_C9), used as stabilizers and templates for obtaining different size and shape of gold nanoparticles. The samples obtained were examined using transmission electron microscopy (TEM), small angle scattering of synchrotron radiation (SAXS), UV-vis spectroscopy and NMR PFG spectroscopy. For the obtained solutions of nanoparticles the plasmon resonance was observed at the wavelengths corresponding to the presence of gold nanoparticles of sizes ranging from 5-100 nm, with a significant shift towards higher wavelength for the samples prepared with addition of dicationic surfactants. TEM images evidence the presence of gold nanoparticles with tetrahedral and spherical morphology in solutions prepared with the surfactants IMI_PROP_C4_C12, IMI_NO3_C4_C12, and those of spherical morphology, but strongly aggregated, in the solution with the cationic surfactant IMI_Cl_oxyC7_C9.

  7. Impact of slow gold clusters on various solids

    International Nuclear Information System (INIS)

    A liquid metal ion source has been installed on a pulsed ion gun. The time of flight (TOF) spectra of the pulsed beam were recorded. With the gold source several cluster ions (up to 10 atoms in the cluster) and doubly charged ions were identified in the ion beam TOF spectra. With a second pulsation, single cluster ions can be selected as projectiles for secondary ion TOF mass spectrometry. The secondary ion emission induced by cluster impact from a variety of targets (organic, CsI, metallic) was studied. A large enhancement of yield is observed by comparison to single atomic ion impact (e.g., a factor of 30 between Au3+ and Au+). The secondary ion yields increase nonlinearly with the number of constituents in the cluster. A comparison with other types of clusters and also fission fragments of 252Cf has been performed. The rate of secondary emission stimulated by cluster is similar to the secondary ion yield induced by fission fragments. (author) 47 refs., 18 figs., 5 tabs

  8. Density functional study on structural and electronic properties of bimetallic gold-yttrium clusters: comparison with pure gold and yttrium clusters

    Institute of Scientific and Technical Information of China (English)

    Mao Hua-Ping; Wang Hong-Yan; Sheng Yong

    2008-01-01

    Employing first-principles methods, based on the density functional theory, this paper investigates the ground state geometric and electronic properties of pure gold clusters, pure yttrium clusters and gold clusters doped each with one yttrium atom. It is shown that the average bond lengths in the Aun-lY(n ≤9) bimetallic clusters are shorter than those in the corresponding pure gold and yttrium clusters. The most stable isomers of the yttrium-doped gold clusters tend to equally delocalize valence s, p and d electrons of the constituent atoms over the entire structure. The Y atom has maximum number of neighbouring Au atom, which tends to be energetically favourable in the lowest-energy equilibrium structures, because the Au-Y bond is stronger than the Au-Au bond. The three-dimensional isomers of Aun-1Y structures are found in an early appearance starting at n=5 (Au4Y). Calculated vertical ionization potential and electron affinities as a function of the cluster size show odd-even oscillatory behaviour, and resemble pure gold clusters. However, one of the most striking feature of pure yttrium clusters is the absence of odd-even alternation, in agreement with mass spectrometric observations. The HOMO-LUMO gap of Au3Y is the biggest in all the doped Aun-1Y(n≤9) bimetallic clusters.

  9. Size-dependent mobility of gold nano-clusters during growth on chemically modified graphene

    International Nuclear Information System (INIS)

    Gold nano-clusters were grown on chemically modified graphene by direct sputter deposition. Transmission electron microscopy of the nano-clusters on these electron-transparent substrates reveals an unusual bimodal island size distribution (ISD). A kinetic Monte Carlo model of growth incorporating a size-dependent cluster mobility rule uniquely reproduces the bimodal ISD, providing strong evidence for the mobility of large clusters during surface growth. The cluster mobility exponent of −5/3 is consistent with cluster motion via one-dimensional diffusion of gold atoms around the edges of the nano-clusters

  10. Size-dependent mobility of gold nano-clusters during growth on chemically modified graphene

    Directory of Open Access Journals (Sweden)

    Gavin R. Bell

    2014-01-01

    Full Text Available Gold nano-clusters were grown on chemically modified graphene by direct sputter deposition. Transmission electron microscopy of the nano-clusters on these electron-transparent substrates reveals an unusual bimodal island size distribution (ISD. A kinetic Monte Carlo model of growth incorporating a size-dependent cluster mobility rule uniquely reproduces the bimodal ISD, providing strong evidence for the mobility of large clusters during surface growth. The cluster mobility exponent of −5/3 is consistent with cluster motion via one-dimensional diffusion of gold atoms around the edges of the nano-clusters.

  11. Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

    OpenAIRE

    Kiefe, Claude; Bestgen, Sebastian; Gamer, Michael T.; Lebedkin, Sergei; Kappes, Manfred M.; Roesky, Peter W.

    2015-01-01

    Phenylpropynyl-functionalized imidazolium salts, as well as their gold complexes, were prepared in excellent yields affording suitable starting materials for metal cluster synthesis. The reactions of these gold complexes with coinage metal phenylacetylides [M(CCPh)]x (M = Cu, Ag) resulted in the formation of novel heterometallic hexanuclear clusters which exhibit mixed metallophillic interactions and intense white photoluminescence at low temperature.

  12. Thermal desorption of oxygen from near-stoichiometric cationic vanadium oxide clusters

    Science.gov (United States)

    Kurokawa, Hodaka; Mafuné, Fumitaka

    2016-05-01

    Oxygen desorption from cationic vanadium oxide clusters, VnOm+ (n = 2-10), composed of a near-stoichiometric (n:m = 2:5) frame with excess oxygen attached was investigated in a thermal energy region by time-of-flight mass spectrometry and thermal desorption spectrometry. Oxygen molecules were observed to desorb from the clusters during heating. The activation energy for desorption was estimated from the temperature dependence of different clusters and exhibited an even-odd alternation with respect to the cluster size, n. This alternation can be explained in terms of oxidation states of the vanadium atoms.

  13. Comparative hyperthermia effects of silica–gold nanoshells with different surface coverage of gold clusters on epithelial tumor cells

    Directory of Open Access Journals (Sweden)

    Park SE

    2015-09-01

    Full Text Available Sang-Eun Park,1,* Jaewon Lee,2,* Taeksu Lee,2 Saet-Byeol Bae,1 Byunghoon Kang,2 Yong-Min Huh,3 Sang-Wha Lee,1 Seungjoo Haam,2 1Department of Chemical and Biochemical Engineering, Gachon University, Gyeonggi-Do, Republic of Korea; 2Department of Chemical Engineering, Yonsei University, Seoul, Republic of Korea; 3Department of Radiology, College of Medicine, Yonsei University, Seoul, Republic of Korea *These authors contributed equally to this work Abstract: Silica–gold nanoshell (SGNS, which is a silica core surrounded by a gold layer, was synthesized by seed-mediated coalescence of gold clusters in an electroless plating solution. SGNS variations with different surface coverage of gold clusters were prepared by adjusting the amounts of gold salts in the presence of formaldehyde-reducing agents. Fully covered SGNS (f-SGNS with connected gold clusters exhibited stronger intensity and more redshift of plasmon bands located around 820 nm than those of partially covered SGNS (p-SGNS with disconnected gold clusters. Upon irradiation with near-infrared light (30 W/cm2, 700–800 nm, f-SGNS caused a larger hyperthermia effect, generating a large temperature change (ΔT =42°C, as compared to the relatively small temperature change (ΔT =24°C caused by p-SGNS. The therapeutic antibody, Erbitux™ (ERB, was further conjugated to SGNS for specific tumor cell targeting. The f-ERB-SGNS showed excellent therapeutic efficacy based on the combined effect of both the therapeutic antibody and the full hyperthermia dose under near-infrared irradiation. Thus, SGNS with well-controlled surface morphology of gold shells may be applicable for near-infrared-induced hyperthermia therapy with tunable optical properties. Keywords: gold nanoshell, plasmon resonance, Erbitux, human epithelial cancer, hyperthermia

  14. Divalent Cation-Dependent Formation of Electrostatic PIP2 Clusters in Lipid Monolayers

    OpenAIRE

    Ellenbroek, WG Wouter; Wang, Y-H; Christian, DA; Discher, DE; Janmey, PA; Liu, AJ

    2011-01-01

    Polyphosphoinositides are among the most highly charged molecules in the cell membrane, and the most common polyphosphoinositide, phosphatidylinositol-4,5-bisphosphate (PIP2), is involved in many mechanical and biochemical processes in the cell membrane. Divalent cations such as calcium can cause clustering of the polyanionic PIP2, but the origin and strength of the effective attractions leading to clustering has been unclear. In addition, the question of whether the ion-mediated attractions ...

  15. Latent image generation by soft landing of size-selected silver cluster cations

    International Nuclear Information System (INIS)

    We investigate the role of silver clusters in the photographic latent image generation. Silver cluster cations were produced in a sputtering arrangement, mass selected by a quadrupole mass filter and deposited with a well controlled kinetic energy onto photographic silver bromide crystals. The fraction of developed crystals after exposure of the samples to photographic developer was measured as a function of the size of the deposited clusters, the cluster coverage, the kinetic energy of the clusters, and the redox-potential of the developer. Development was observed after deposition of Ag4+ or larger aggregates, and, to a much lower extend, after deposition of the trimer. Silver monomers and dimers showed no photographic effect. Our data confirm that silver clusters above a critical size, which depends on the redox-potential of the developer, form the latent image in photography. (author)

  16. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

    International Nuclear Information System (INIS)

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N+ clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N+ clusters decreases as the N increases, and it is higher than that of (V 2O5)N+ for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N+ (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion

  17. Lipid Reconstitution-Enabled Formation of Gold Nanoparticle Clusters for Mimetic Cellular Membrane

    OpenAIRE

    Jiyoung Nam; Yong-Tae Kim; Aeyeon Kang; Kook-Han Kim; KyoRee Lee; Wan Soo Yun; Yong Ho Kim

    2016-01-01

    Gold nanoparticles (AuNPs) encapsulated within reconstituted phospholipid bilayers have been utilized in various bioapplications due to their improved cellular uptake without compromising their advantages. Studies have proved that clustering AuNPs can enhance the efficacy of theranostic effects, but controllable aggregation or oligomerization of AuNPs within lipid membranes is still challenging. Here, we successfully demonstrate the formation of gold nanoparticle clusters (AuCLs), supported b...

  18. Enantiopure Radical Cation Salt Based on Tetramethyl-Bis(ethylenedithio-Tetrathiafulvalene and Hexanuclear Rhenium Cluster

    Directory of Open Access Journals (Sweden)

    Flavia Pop

    2016-01-01

    Full Text Available Electrocrystallization of the (S,S,S,S enantiomer of tetramethyl-bis(ethylenedithio-tetrathiafulvalene donor 1 in the presence of the dianionic hexanuclear rhenium (III cluster [Re6S6Cl8]2− affords a crystalline radical cation salt formulated as [(S-1]2·Re6S6Cl8, in which the methyl substituents of the donors adopt an unprecedented all-axial conformation. A complex set of intermolecular TTF···TTF and cluster···TTF interactions sustain an original tridimensional architecture.

  19. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    Science.gov (United States)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

  20. Geometry, chemical reactivity and Raman spectra of gold clusters

    OpenAIRE

    Ngangbam Bedamani Singh; Utpal Sarkar

    2015-01-01

    Structures, stability, and chemical reactivity of Aun (n = 2-10) clusters are investigated using density functional theory (DFT). We have studied the reactivity parameters of the clusters in terms of relevant electronic structure principles. It is observed that stability and properties are strongly dependent on the cluster size. Clusters with an even number of atoms are found to be energetically and chemically more stable than odd-numbered clusters. Electronic structure of clusters has been i...

  1. Infrared Photodissociation Spectra of Mass-Selected Homoleptic Dinuclear Palladium Carbonyl Cluster Cations in the Gas Phase

    Institute of Scientific and Technical Information of China (English)

    崔洁铭; 邢小鹏; 池超贤; 王冠军; 刘智攀; 周鸣飞

    2012-01-01

    Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2(CO)n (n=5 8) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2(CO)+ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2(CO)6+ and Pd2(CO)7+ cations are determined to involve one weakly semibridging CO group. The Pd2(CO)8+ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a Pd--Pd half bond. The Pd--Pd distance increases with the number of CO ligands.

  2. Single-step co-deposition of nanostructured tungsten oxide supported gold nanoparticles using a gold–phosphine cluster complex as the gold precursor

    International Nuclear Information System (INIS)

    The use of a molecular gold organometallic cluster in chemical vapour deposition is reported, and it is utilized, together with a tungsten oxide precursor, for the single-step co-deposition of (nanostructured) tungsten oxide supported gold nanoparticles (NPs). The deposited gold-NP and tungsten oxide supported gold-NP are highly active catalysts for benzyl alcohol oxidation; both show higher activity than SiO2 supported gold-NP synthesized via a solution-phase method, and tungsten oxide supported gold-NP show excellent selectivity for conversion to benzaldehyde. (paper)

  3. Cluster-Continuum Calculations of Hydration Free Energies of Anions and Group 12 Divalent Cations

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Hao-Bo [ORNL; Liang, Liyuan [ORNL; Parks, Jerry M [ORNL; Smith, Jeremy C [ORNL; Riccardi, Demian M [ORNL; Gu, Baohua [ORNL

    2013-01-01

    Understanding aqueous phase processes involving group 12 metal cations is relevant to both environmental and biological sciences. Here, quantum chemical methods and polarizable continuum models are used to compute the hydration free energies of a series of divalent group 12 metal cations (Zn2+, Cd2+, and Hg2+) together with Cu2+ and the anions OH , SH , Cl , and F . A cluster-continuum method is employed, in which gas-phase clusters of the ion and explicit solvent molecules are immersed in a dielectric continuum. Two approaches to define the size of the solute-water cluster are compared, in which the number of explicit waters used is either held constant or determined variationally as that of the most favorable hydration free energy. Results obtained with various polarizable continuum models are also presented. Each leg of the relevant thermodynamic cycle is analyzed in detail to determine how different contributions yield the observed mean signed error (MSE) and the standard deviation of the error (STDEV) between theory and experiment. The use of a constant number of water molecules for each set of ions is found to lead to predicted relative trends that benefit from error cancellation. Overall, the best results are obtained with MP2 and the Solvent Model D polarizable continuum model (SMD), with eight explicit water molecules for anions and ten for the metal cations, yielding a STDEV of 2.3 kcal/mol and MSE of 0.9 kcal/mol between theoretical to experimental hydration free energies, which range from -72.4 kcal/mol for SH to -505.9 kcal/mol for Cu2+. Using B3PW91 with DFT-D3 dispersion corrections (B3PW91-D) and SMD yields a STDEV of 3.3 kcal mol 1 and MSE of 1.6 kcal/mol, to which adding MP2 corrections from smaller divalent metal ion water molecule clusters yields very good agreement with the full MP2 results. Using B3PW91-D and SMD, with two explicit water molecules for anions and six for divalent metal cations also yields reasonable agreement with experiment

  4. Theoretical study of the thermally induced structural fluctuations in sub-nanometre size gold clusters

    Science.gov (United States)

    Cabrera-Trujillo, José Manuel; Martín Montejano-Carrizales, Juan; Aguilera-Granja, Faustino; Posada-Amarillas, Álvaro

    2015-07-01

    A reactive potential model and the classical molecular dynamics method (RMD) have been used to study the structure and energetics of sub-nanometre size gold clusters through well-known structural models reported in the literature for AuN, with N = 19, 20 and 21 atoms. After several simulated-annealing simulations for temperatures up to 1500 K, the AuN clusters clearly evolve to well-defined structures at room temperature. For the studied gold clusters, the low-lying structures are single- and double-icosahedra with mobile atoms on the surface, in agreement with experimental results on sub-nanometre size gold clusters exhibiting shape oscillations at room temperature and also with those involved in the design of molecules based on gold superatoms [J.-I. Nishigaki, K. Koyasu, T. Tsukuda, Chem. Rec. 14, 897 (2014)]. The evolution of the structural stability of the AuN clusters under exceptional thermal conditions is analysed by comparing the size and temperature variations of the centrosymmetry parameter and the potential energy. A key understanding of the various possible structural changes undergone by these tiny particles is thus developed. The usefulness of the RMD to study nanometre or sub-nanometre size gold clusters is shown.

  5. Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    The melting behavior of bimetallic gold-platinum nanoclusters is studied by applying Brownian-type isothermal molecular dynamics (MD) simulation, a program modified from the cubic coupling scheme (CCS). The process begins with the ground-state structures obtained from global minimum search algorithm and proceeds with the investigation of the effect of temperature on the thermal properties of gold-platinum nanoalloy clusters. N-body Gupta potential has been employed in order to account for the interactions between gold and platinum atoms. The ground states of the nanoalloy clusters, which are core-shell segregated, are heated until they become thermally segregated. The detailed melting mechanism of the nanoalloy clusters is studied via this approach to provide insight into the thermal stability of the nanoalloy clusters.

  6. Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

    International Nuclear Information System (INIS)

    The melting behavior of bimetallic gold-platinum nanoclusters is studied by applying Brownian-type isothermal molecular dynamics (MD) simulation, a program modified from the cubic coupling scheme (CCS). The process begins with the ground-state structures obtained from global minimum search algorithm and proceeds with the investigation of the effect of temperature on the thermal properties of gold-platinum nanoalloy clusters. N-body Gupta potential has been employed in order to account for the interactions between gold and platinum atoms. The ground states of the nanoalloy clusters, which are core-shell segregated, are heated until they become thermally segregated. The detailed melting mechanism of the nanoalloy clusters is studied via this approach to provide insight into the thermal stability of the nanoalloy clusters

  7. Cd/Hg cationic substitution in magic-sized CdSe clusters: Optical characterization and theoretical studies

    International Nuclear Information System (INIS)

    Highlights: • HgSe magic-sized clusters were prepared via Cd/Hg cationic exchange in pyridine. • Upon cationic exchange CdSe clusters behave differently from quantum dots or rods. • Theoretical calculations of magic-sized clusters agree well with experimental data. - Abstract: We examine conversion of magic-sized CdSe clusters (MSCs) into HgSe ones by means of Cd/Hg cation exchange. With this procedure Cd8Cd17– and Cd32–selenide clusters can be converted into corresponding Hg8–, Hg17– and Hg32–selenide ones. Upon cationic exchange MSCs behavior differs from that of bulkier counterparts – larger (2–3 nm) quantum dots. Unlike CdSe colloidal quantum dots, magic-sized clusters are converted in fast and complete manner without a formation of intermediate mixed CdxHg1−x compounds that was established on the basis of optical absorption spectroscopy and chemical composition analysis. These assumptions were supported by DFT quantum chemical calculations performed for Cd8–, Cd17– and Hg8–, Hg17–selenide model clusters. Energies of experimental and calculated optical transitions were compared in order to prove the isostructural character of cationic substitution in magic-sized clusters

  8. Femtosecond-laser photoemission and photodesorption from magnesia supported gold clusters

    Energy Technology Data Exchange (ETDEWEB)

    Vaida, Mihai E.; Gleitsmann, Tobias; Tchitnga, Robert; Bernhardt, Thorsten M. [Institute of Surface Chemistry and Catalysis, University of Ulm (Germany)

    2010-05-15

    Nanosize gold clusters were grown by thermal evaporation on ultrathin magnesia films on Mo(100) and investigated by femtosecond (fs)-laser photoemission spectroscopy. The surface work function in this system was found to increase with increasing nominal gold coverage. Methyl bromide (CH{sub 3}Br) molecules adsorb molecularly on the magnesia surface as well as on the gold clusters. At sub-monolayer coverage the CH{sub 3}Br molecules were, however, considerably stronger bound to the gold particles than to the magnesia surface as revealed by temperature programmed desorption spectroscopy. To investigate the photoreaction dynamics of the adsorbate molecules fs-laser pump-probe mass spectrometry was applied. In this new approach the methyl fragment appearance was monitored after photoexcitation of the adsorbed CH{sub 3}Br with fs time resolution. The transient methyl data revealed that the CH{sub 3}Br dissociation and subsequent methyl desorption proceeded in less than one picosecond. Most interestingly, a part of the transient signal could be unambiguously assigned to the dynamics of methyl desorption from the gold clusters. The appearance of this signal at about 270 fs after photoexcitation illustrates the massive distortion of the CH{sub 3}Br electronic level structure due to the strong interaction with the gold clusters compared to the bare magnesia surface. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  9. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides.

    Science.gov (United States)

    Ding, Xun-Lei; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N(+) clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N(+) clusters decreases as the N increases, and it is higher than that of (V 2O5)N(+) for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N(+) (N = 2-6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion. PMID:26429016

  10. MODIFICATION OF TRANSITION METAL CATIONS TO POLYMER- STABILIZED PLATINUM COLLOIDAL CLUSTERS IN ENANTIOSELECTIVE HYDROGENATION OF METHYL PYRUVATE

    Institute of Scientific and Technical Information of China (English)

    Xiao-ping Yan; Bao-lin He; Jie Zhang; Han-fan Liu

    2005-01-01

    Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate. Compared to the enantiomeric excess (e.e.) value (71.4%)obtained without the presence of metal cations, obvious e.e. enhancement (up to 82.5%) was resulted from the addition of Zn2+ but with a certain decrease in activity. The reaction parameters in the presence of Zn2+ were also studied. It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

  11. Optical absorption by magnesia-supported gold clusters and nanocatalysts: effects from the support, cluster and adsorbants

    CERN Document Server

    Walter, M; Walter, Michael; H\\"akkinen, Hannu

    2005-01-01

    Polarization-resolved optical spectra of magnesia-supported gold clusters Au$_N$/MgO (N=1,2,4,8), bound at a surface color center $F_s$ of the MgO(100) face, are calculated from the time-dependent density functional theory. The optical lines for n=1,2 are dominated by transitions that involve strong hybridization between gold and $F_s$ states whereas for n=4,8 intracluster transitions dominate. The theoretical optical spectra are sensitive to cluster structure and adsorbants (here CO and O$_2$ molecules on Au$_8$/MgO) which suggests polarization-resolved optical spectroscopy as a powerful tool to investigate structures and functions of chemically active, supported clusters.

  12. Sputtering of clusters from copper-gold alloys

    International Nuclear Information System (INIS)

    Polycrystalline Cu, Cu20Au80, Cu40Au60, Cu80Au20 and Au samples were bombarded with 15 keV Ar+, and the resulting secondary neutral yield distribution was studied by non-resonant laser post-ionisation mass spectrometry. Neutral clusters containing up to 15 atoms were observed for the targets. The yield of neutral clusters, CumAun-m, containing n atoms, Yn, was found to follow a power in n, i.e. Yn∝n-δ, where the exponent δ varied from 5.2 to 10.1. For a fixed n, the cluster yields showed a variation with number of copper atoms, m, much greater than expected for a binomial distribution suggesting that the clusters are not formed randomly above the surface and a component of preformed cluster emission occurs. In addition, the cluster compositions from the sputtered alloys were indicative of sputtering from a copper rich surface.

  13. Infrared photodissociation spectroscopy of mass-selected silver and gold nitrosyl cation complexes.

    Science.gov (United States)

    Li, Yuzhen; Wang, Lichen; Qu, Hui; Wang, Guanjun; Zhou, Mingfei

    2015-04-16

    The [M(NO)n](+) cation complexes (M = Au and Ag) are studied for exploring the coordination and bonding between nitric oxide and noble metal cations. These species are produced in a laser vaporization supersonic ion source and probed by infrared photodissociation spectroscopy in the NO stretching frequency region using a collinear tandem time-of-flight mass spectrometer. The geometric and electronic structures of these complexes are determined by comparison of the distinctive experimental spectra with simulated spectra derived from density functional theory calculations. All of these noble metal nitrosyl cation complexes are characterized to have bent NO ligands serving as one-electron donors. The spectrum of [Au(NO)2Ar](+) is consistent with 2-fold coordination with a near linear N-Au-N arrangement for this ion. The [Au(NO)n](+) (n = 3-4) cations are determined to be a mixture of 2-fold coordinated form and 3- or 4-fold coordinated form. In contrast, the spectra of [Ag(NO)n](+) (n = 3-6) provide evidence for the completion of the first coordination shell at n = 5. The high [Au(NO)n](+) and [Ag(NO)n](+) (n ≥ 3 for Au, n ≥ 4 for Ag) complexes each involve one or more (NO)2 dimer ligands, as observed in the copper nitrosyl cation complexes, indicating that ligand-ligand coupling plays an important role in the structure and bonding of noble metal nitrosyl cation complexes. PMID:25811327

  14. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    Science.gov (United States)

    Liu, Siqi; Xu, Yi-Jun

    2016-01-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

  15. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    Science.gov (United States)

    Liu, Siqi; Xu, Yi-Jun

    2016-03-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

  16. An insight into the optical properties of a sub nanosize glutathione stabilized gold cluster.

    Science.gov (United States)

    Nair, Lakshmi V; Nair, Resmi V; Jayasree, Ramapurath S

    2016-07-28

    In this study, gold quantum clusters with distinct fluorescence properties were developed and their structural and physical behaviour was evaluated. The clusters were prepared by etching gold nanoparticles with glutathione. Three different Au33 clusters with emission profiles in the NIR region and one blue emitting cluster, Au8 were developed by varying the geometrical arrangement of atoms within the cluster. These clusters having sizes in the range of 0.7 to 2 nm were synthesized by choosing different reaction temperatures from 0 °C to 70 °C and pH between 1.5 and 10. In the three cases, formation of self assembled atoms within the cluster and the corresponding changes in optical properties were observed. A detailed evaluation of the number of atoms and the core-ligand ratio using MALDI-MS and a change in the binding energy as seen in the XPS study confirmed this finding. The study demonstrates that the self assembly of atoms and their arrangement is an important factor in determining the characteristics of the cluster. In this communication, we put forward a new concept where the number of atoms and their arrangement within the clusters play a crucial role in tuning their optical properties. PMID:27356966

  17. Preparation of multi-coloured different sized fluorescent gold clusters from blue to NIR, structural analysis of the blue emitting Au7 cluster, and cell-imaging by the NIR gold cluster

    Science.gov (United States)

    Roy, Subhasish; Baral, Abhishek; Bhattacharjee, Rameswar; Jana, Batakrishna; Datta, Ayan; Ghosh, Surajit; Banerjee, Arindam

    2015-01-01

    Blue, green, orange-red, red and NIR emitting gold quantum clusters have been prepared in aqueous media by using a bioactive peptide glutathione (reduced) at physiological pH. Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) analyses show that the core structure sizes of the five different gold clusters are Au7 (blue), Au16 (green), Au19 (orange-red), Au21 (red) and Au22 (NIR). The photo-stability and pH-stability of these quantum clusters have been measured, and these are photo-stable against continuous UV irradiation for a few hours. They also exhibit moderate to good pH-stability within the pH range of 5-12.5. A computational study reveals the organisation of gold atoms in the thiolate-protected blue quantum cluster and its several structural parameters, including the mode of interaction of ligand molecules with Au atoms in the Au7 cluster. Interestingly, it has been found that NIR emitting gold quantum cluster can easily be internalized into the adenocarcinomic human alveolar basal epithelial cell line (A549 cell line). Moreover, a MTT assay indicates that our NIR emitting gold quantum cluster show very low cytotoxicy to A549 cancer cells.Blue, green, orange-red, red and NIR emitting gold quantum clusters have been prepared in aqueous media by using a bioactive peptide glutathione (reduced) at physiological pH. Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) analyses show that the core structure sizes of the five different gold clusters are Au7 (blue), Au16 (green), Au19 (orange-red), Au21 (red) and Au22 (NIR). The photo-stability and pH-stability of these quantum clusters have been measured, and these are photo-stable against continuous UV irradiation for a few hours. They also exhibit moderate to good pH-stability within the pH range of 5-12.5. A computational study reveals the organisation of gold atoms in the thiolate-protected blue quantum cluster and its several

  18. Structures, stabilities, and electronic properties for rare-earth lanthanum doped gold clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Ya-Ru [Baoji University of Arts and Sciences (China). Dept. of Physics and Information Technology

    2015-07-01

    The structures, stabilities, and electronic properties of rare-earth lanthanum doped gold La{sub 2}Au{sub n} (n = 1-9) and pure gold Au{sub n} (n ≤ 11) clusters have been investigated by using density functional theory. The optimized geometries show that the lowest energy structures of La{sub 2}Au{sub n} clusters favour the 3D structure at n ≥ 3. The lanthanum atoms can strongly enhance the stabilities of gold clusters and tend to occupy the most highly coordinated position. By analysing the gap, vertical ionization potential, and chemical hardness, it is found that the La{sub 2}Au{sub 6} isomer possesses higher stability for small-sized La{sub 2}Au{sub n} clusters (n = 1-9). The charges in the La{sub 2}Au{sub n} clusters transfer from La atoms to the Au{sub n} host. In addition, Wiberg bond indices analysis reveals that the intensity of different bonds of La{sub 2}Au{sub n} clusters exhibits a sequence of La-La bond > La-Au bond > Au-Au bond.

  19. The RedGOLD cluster detection algorithm and its cluster candidate catalogue for the CFHT-LS W1

    Science.gov (United States)

    Licitra, Rossella; Mei, Simona; Raichoor, Anand; Erben, Thomas; Hildebrandt, Hendrik

    2016-01-01

    We present RedGOLD (Red-sequence Galaxy Overdensity cLuster Detector), a new optical/NIR galaxy cluster detection algorithm, and apply it to the CFHT-LS W1 field. RedGOLD searches for red-sequence galaxy overdensities while minimizing contamination from dusty star-forming galaxies. It imposes an Navarro-Frenk-White profile and calculates cluster detection significance and richness. We optimize these latter two parameters using both simulations and X-ray-detected cluster catalogues, and obtain a catalogue ˜80 per cent pure up to z ˜ 1, and ˜100 per cent (˜70 per cent) complete at z ≤ 0.6 (z ≲ 1) for galaxy clusters with M ≳ 1014 M⊙ at the CFHT-LS Wide depth. In the CFHT-LS W1, we detect 11 cluster candidates per deg2 out to z ˜ 1.1. When we optimize both completeness and purity, RedGOLD obtains a cluster catalogue with higher completeness and purity than other public catalogues, obtained using CFHT-LS W1 observations, for M ≳ 1014 M⊙. We use X-ray-detected cluster samples to extend the study of the X-ray temperature-optical richness relation to a lower mass threshold, and find a mass scatter at fixed richness of σlnM|λ = 0.39 ± 0.07 and σlnM|λ = 0.30 ± 0.13 for the Gozaliasl et al. and Mehrtens et al. samples. When considering similar mass ranges as previous work, we recover a smaller scatter in mass at fixed richness. We recover 93 per cent of the redMaPPer detections, and find that its richness estimates is on average ˜40-50 per cent larger than ours at z > 0.3. RedGOLD recovers X-ray cluster spectroscopic redshifts at better than 5 per cent up to z ˜ 1, and the centres within a few tens of arcseconds.

  20. Gold-cluster ranges in aluminium, silicon and copper

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, H.H. E-mail: nimb@fys.ku.dk; Johansen, A.; Olsen, M.; Touboltsev, V

    2003-12-01

    Single atom Au and Au{sub 2}, Au{sub 3} and Au{sub 7} clusters with energies of 10-100 keV/atom have been implanted at low fluence into Al, Si and Cu targets, the Au{sub 7} clusters only at 44.3 keV/atom into Si. The range distributions were analyzed by oblique (15 deg. ) incidence RBS. In no case was the range found to be different for the cluster implant from that of the atomic implant at equal velocity, implying the nuclear stopping to be identical, but the 10 keV/atom implant in Cu showed the cluster distributions to be substantially broader than those of the atomic implants. The energies were thus too high to observe a possible 'clearing the way' effect, but the Cu results hint at a 'within spike' diffusion mechanism.

  1. Moessbauer studies of non-linear excitations and gold cluster compounds

    International Nuclear Information System (INIS)

    Moessbauer effect spectroscopy has been applied to the study of three polynuclear gold cluster compounds. The resulting information on the local vibrational density of states has been compared to several models which take the finite size of the particles into consideration. 188 refs.; 34 figs.; 103 schemes; 8 tabs

  2. Sputtering of clusters from copper-gold alloys

    Energy Technology Data Exchange (ETDEWEB)

    King, B.V. [University of Newcastle, School of Mathematical and Physical Sciences, Callaghan 2308, NSW (Australia)], E-mail: bruce.king@newcastle.edu.au; Moore, J.F. [Argonne National Laboratory, Materials Science Division, 9700 S. Cass Ave., Argonne, IL 60439 (United States); MassThink LLC, Naperville, IL 60565 (United States); Zinoviev, A.V.; Veryovkin, I.V.; Pellin, M.J. [Argonne National Laboratory, Materials Science Division, 9700 S. Cass Ave., Argonne, IL 60439 (United States)

    2009-08-15

    Polycrystalline Cu, Cu{sub 20}Au{sub 80}, Cu{sub 40}Au{sub 60}, Cu{sub 80}Au{sub 20} and Au samples were bombarded with 15 keV Ar{sup +}, and the resulting secondary neutral yield distribution was studied by non-resonant laser post-ionisation mass spectrometry. Neutral clusters containing up to 15 atoms were observed for the targets. The yield of neutral clusters, Cu{sub m}Au{sub n-m}, containing n atoms, Y{sub n}, was found to follow a power in n, i.e. Y{sub n}{proportional_to}n{sup -{delta}}, where the exponent {delta} varied from 5.2 to 10.1. For a fixed n, the cluster yields showed a variation with number of copper atoms, m, much greater than expected for a binomial distribution suggesting that the clusters are not formed randomly above the surface and a component of preformed cluster emission occurs. In addition, the cluster compositions from the sputtered alloys were indicative of sputtering from a copper rich surface.

  3. Synthesis of cationic hyperbranched multiarm copolymer and its application in self-reducing and stabilizing gold nanoparticles

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A novel hyperbranched multiarm copolymer of HBPO-star-PDEAEMA with a hydrophobic poly(3-ethyl-3-(hydroxymethyl) oxetane)(HBPO) core and many cationic poly(2-(N,N-diethylamino) ethyl methacrylate)(PDEAEMA) arms has been synthesized through an atom transfer radical polymerization(ATRP) method,and been applied to spontaneously reduce and stabilize gold nanoparticles(AuNPs) in water without other additional agents.The size of the nanoparticles could be effectively controlled at about 4 nm,and the nanoparticles are extremely stable in solution without aggregation even for one year.It was found that solution pH and the molar ratio of N/Au have certain effects on the size and stability of AuNPs.This work provides a simple method for the synthesis of uniform and highly stable AuNPs.

  4. Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

    Institute of Scientific and Technical Information of China (English)

    YIN Shi; MA YanPing; DU Lin; HE ShengGui; GE MaoFa

    2008-01-01

    The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters (VmO+n) toward acetylene (C2H2) molecules under gas phase (P, ~ 1.14 kPa), under near room temperature (T, ~ 350 K) conditions. Association products, VmOnC2H+2 (m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13;6,13-16, and 7,17), are observed. The oxidation of C2H2 by (V2O5)+n, (n = 1-3) is experimentally identified.The reactivity of (V2O5)+n decreases as n increases. Density functional theory (DFT) calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O+5 can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V2O6C2H+2 and nonobservation of V2O7,8C2H+2 in the experiments are also well interpreted based on the DFT calculations.The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.

  5. Immunosorbent assay using gold colloid cluster technology for determination of IgEs in patients’ sera

    Directory of Open Access Journals (Sweden)

    Haifa Al-Dubai

    2010-10-01

    Full Text Available Haifa Al-Dubai1, Irene Lichtscheidl2, Martina Strobl1, Gisela Pittner1, Fritz Pittner11Department of Biochemistry, Max F Perutz Laboratories, University of Vienna, Vienna, Austria; 2Institute of Cell Imaging and Ultrastructure Research, Vienna, AustriaAbstract: This study focuses on the development of a sensitive and simple cluster-linked immunosorbent assay (CLISA using gold colloidal cluster labeling for determination of proteins such as antigens (Ags or antibodies (Abs. Abs for detection can be labeled with gold colloid clusters (GCCs. The Fc domain of the Abs binds to the clusters, and the Fab domain to the Ag on a nitrocellulose membrane or a microtiter plate as a support for dot-blotting. The signal of positive interaction between GCC-labeled Abs and its dotted Ag is detectable by the naked eye and can be quantified by comparison to a color scale prepared from a dilution series of known sample concentrations. The colored reaction product is stable for prolonged periods and does not fade, making this method a simple, fast, and convenient means for detection of Ag or Ab biorecognitions and an alternative to enzyme-linked immunosorbent assay. Several interactions between different Ags or Abs (eg, ß-lactoglobulin and solutions avoiding gold colloidal cluster flocculation (eg, using protein G were studied. CLISA was tested for other analytical purposes such as detection of IgEs in patients’ sera.Keywords: ELISA, allergen, patient sera, CLISA, immunoassay, ß-lactoglobulin

  6. Magnetic Moments of Chromium-Doped Gold Clusters: The Anderson Impurity Model in Finite Systems

    CERN Document Server

    Hirsch, K; Langenberg, A; Niemeyer, M; Langbehn, B; Möller, T; Terasaki, A; Issendorff, B v; Lau, J T

    2013-01-01

    The magnetic moment of a single impurity atom in a finite free electron gas is studied in a combined x-ray magnetic circular dichroism spectroscopy and density functional theory study of size-selected free chromium-doped gold clusters. The observed size-dependence of the local magnetic moment can essentially be understood in terms of the Anderson impurity model. Electronic shell closure in the host metal minimizes the interaction of localized impurity states with the confined free electron gas and preserves the full magnetic moment of $\\unit[5]{\\mu_B}$ in $\\mathrm{CrAu}_{2}^{+}$ and $\\mathrm{CrAu}_{6}^{+}$ clusters. Even for open-shell species, large local moments are observed that scale with the energy gap of the gold cluster. This indicates that an energy gap in the free electron gas generally stabilizes the local magnetic moment of the impurity.

  7. Ultrasensitive aptamer biosensor for malathion detection based on cationic polymer and gold nanoparticles.

    Science.gov (United States)

    Bala, Rajni; Kumar, Munish; Bansal, Kavita; Sharma, Rohit K; Wangoo, Nishima

    2016-11-15

    In this work, we have demonstrated a novel sensing strategy for an organophosphorus pesticide namely, malathion, employing unmodified gold nanoparticles, aptamer and a positively charged, water-soluble polyelectrolyte Polydiallyldimethylammonium chloride (PDDA). The PDDA when associated with the aptamer prevents the aggregation of the gold-nanoparticles while no such inhibition is observed when the aptamer specific pesticide is added to the solution, thereby changing the color of the solution from red to blue. This type of biosensor is quite simple and straightforward and can be completed in a few minutes without the need of any expensive equipment or trained personnel. The proposed method was linear in the concentration range of 0.5-1000pM with 0.06pM as the limit of detection. Moreover, the proposed assay selectively recognized malathion in the presence of other interfering substances and thus, can be applied to real samples for the rapid screening of malathion. PMID:27208476

  8. Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

    Institute of Scientific and Technical Information of China (English)

    WANG ZheChen; DING XunLei; MA YanPing; CAO Hai; WU XiaoNan; ZHAO YanXia; HE ShengGui

    2009-01-01

    Density functional theory (DFT) study of reaction between vanadium trioxide cluster cation (VO+3) and ethylene (C2H4) to yield VO+2 + CH3CHO (acetaldehyde) and VO2CH+2 + HCHO (formaldehyde) is carried out.Structures of all reactants,products,intermediates,and transition state in the reaction have been optimized and characterized.The results show unexpected barriers in the reaction due to the existence of a η2-O2 moiety in the ground state structure of VO+3.The initial reaction steps combining ethylene adsorption,C=C activation and O-O cleavage are proposed as rate limiting processes.Comparison of reactions of VO+3 + C2H4 with VO3 + C2H4 and VO+2 + C2H4 in the previous studies is made in detail.The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.

  9. Growth of fluorescence gold clusters using photo-chemically activated ligands

    Science.gov (United States)

    Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

    2016-03-01

    Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

  10. First principle study of the interaction of elemental Hg with small neutral, anionic and cationic Pd ( = 1-6) clusters

    Indian Academy of Sciences (India)

    Shamoon Ahmad Siddiqui; Nadir Bouarissa

    2013-11-01

    Density functional theory (DFT)-based calculations have been performed so as to study the interaction of elemental mercury (Hg) with small neutral, cationic and anionic palladium clusters (Pd, = 1-6). Results of these calculations clearly indicate that frontier molecular orbital (FMO) theory is a useful method to predict the selectivity of Hg adsorption. Binding energies of Hg on cationic Pd clusters are generally found to be greater than those on neutral and anionic clusters. Results of natural bond orbital (NBO) analysis show that the flow of electrons in the neutral and charged complexes is mainly due to s orbitals of Hg. NBO analysis also indicates that, in most of the cases, the binding energies of Hg with Pdn clusters are directly proportional to charge transfer, i.e., greater the charge transfer, higher is the binding energy.

  11. Geometries, stabilities, and electronic properties of Be-doped gold clusters: a density functional theory study

    International Nuclear Information System (INIS)

    We have systematically investigated the geometrical structures, relative stabilities and electronic properties of small bimetallic AunBe (n = 1, 2, ..., 8) clusters using a density functional method at BP86 level. The optimized geometries reveal that the impurity beryllium atom dramatically affects the structures of the Aun clusters. The averaged binding energies, fragmentation energies, second-order difference of energies, the highest occupied-lowest unoccupied molecular orbital energy gaps and chemical hardness are investigated. All of them exhibit a pronounced odd—even alternation, manifesting that the clusters with even number of gold atoms possess relatively higher stabilities. Especially, the linear Au2Be cluster is magic cluster with the most stable chemical stability. According to the natural population analysis, it is found that charge-transferring direction between Au atom and Be atom changes at the size of n = 4. (atomic and molecular physics)

  12. Geometries, stabilities, and electronic properties of Be-doped gold clusters: a density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Chen Dong-Dong; Kuang Xiao-Yu; Zhao Ya-Ru; Shao Peng; Li Yan-Fang

    2011-01-01

    We have systematically investigated the geometrical structures, relative stabilities and electronic properties of small bimetallic AunBe (n = 1, 2, ..., 8) clusters using a density functional method at BP86 level. The optimized geometries reveal that the impurity beryllium atom dramatically affects the structures of the Aun clusters. The averaged binding energies, fragmentation energies, second-order difference of energies, the highest occupied-lowest unoccupied molecular orbital energy gaps and chemical hardness are investigated. All of them exhibit a pronounced odd-even alternation,manifesting that the clusters with even number of gold atoms possess relatively higher stabilities. Especially, the linear Au2Be cluster is magic cluster with the most stable chemical stability. According to the natural population analysis, it is found that charge-transferring direction between Au atom and Be atom changes at the size of n = 4.

  13. Permanent magnetism in phosphine- and chlorine-capped gold: from clusters to nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Marquez, Miguel A., E-mail: miguel.angel@icmse.csic.es; Guerrero, Estefania; Fernandez, Asuncion [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain); Crespo, Patricia; Hernando, Antonio [Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC) (Spain); Lucena, Raquel; Conesa, Jose C. [Instituto de Catalisis y Petroleoquimica (CSIC) (Spain)

    2010-05-15

    Magnetometry results have shown that gold NPs ({approx}2 nm in size) protected with phosphine and chlorine ligands exhibit permanent magnetism. When the NPs size decreases down to the subnanometric size range, e.g. undecagold atom clusters, the permanent magnetism disappears. The near edge structure of the X-ray absorption spectroscopy data points out that charge transfer between gold and the capping system occurs in both cases. These results strongly suggest that nearly metallic Au bonds are also required for the induction of a magnetic response. Electron paramagnetic resonance observations indicate that the contribution to magnetism from eventual iron impurities can be disregarded.

  14. Peptide protected gold clusters: chemical synthesis and biomedical applications

    Science.gov (United States)

    Yuan, Qing; Wang, Yaling; Zhao, Lina; Liu, Ru; Gao, Fuping; Gao, Liang; Gao, Xueyun

    2016-06-01

    Bridging the gap between atoms and nanoparticles, noble metal clusters with atomic precision continue to attract considerable attention due to their important applications in catalysis, energy transformation, biosensing and biomedicine. Greatly different to common chemical synthesis, a one-step biomimetic synthesis of peptide-conjugated metal clusters has been developed to meet the demand of emerging bioapplications. Under mild conditions, multifunctional peptides containing metal capturing, reactive and targeting groups are rationally designed and elaborately synthesized to fabricate atomically precise peptide protected metal clusters. Among them, peptide-protected Au Cs (peptide-Au Cs) possess a great deal of exceptional advantages such as nanometer dimensions, high photostability, good biocompatibility, accurate chemical formula and specific protein targeting capacity. In this review article, we focus on the recent advances in potential theranostic fields by introducing the rising progress of peptide-Au Cs for biological imaging, biological analysis and therapeutic applications. The interactions between Au Cs and biological systems as well as potential mechanisms are also our concerned theme. We expect that the rapidly growing interest in Au Cs-based theranostic applications will attract broader concerns across various disciplines.

  15. Gold

    International Nuclear Information System (INIS)

    Present article is devoted to gold content in fluorite. In order to obtain the comprehensive view on gold distribution in fluorite the fluorite formations of various geologic deposits and ores of Kazakhstan, Uzbekistan, Tajikistan, Mongolia, Moldova and some geologic deposits of Russia were studied. The gold content in fluorite of geologic deposits of various mineralogical and genetic type was defined.

  16. Non-linear sputtering effects induced by MeV energy gold clusters

    International Nuclear Information System (INIS)

    Gold clusters Aun+ with 1 < n ≤ 4, accelerated to MeV energies at the Orsay tandem accelerator, have been used to induce secondary ion emission from the surface of thin organic and inorganic films. A non-linear enhancement of the secondary ion yields is observed when cluster impacts are compared to single atom impacts at the same velocity. It has been shown that the collective effects propagate in the solid over a depth larger than 2000 A. The equilibrium charge state of cluster constituents after their passage through a thin carbon foil (1000 A) has been measured. The mean value for the cluster constituents is the same as for single atoms at the same velocity. (authors). 41 refs., 8 figs., 1 tab

  17. Optical Imaging of Cells with Gold Nanoparticle Clusters as Light Scattering Contrast Agents

    DEFF Research Database (Denmark)

    Tanev, Stoyan

    2011-01-01

    This chapter has two main objectives. First, to review a number of examples illustrating the application of the FDTD approach to the modeling of some typical light scattering configurations that could be associated with flow cytometry. Second, to provide a thorough discussion of these new develop...... from OPCM imaging of single biological cells in conditions of controlled refractive index matching (RIM) and labeling by diffused and clustered gold NPs. The chapter concludes with a discussion and suggestions for future research....

  18. Collision-induced dissociation of Co+n (n=2--18) with Xe: Bond energies of cationic and neutral cobalt clusters, dissociation pathways, and structures

    International Nuclear Information System (INIS)

    The kinetic energy dependence of collision-induced dissociation (CID) of Co+n (n=2--18) with xenon is studied by using a guided ion beam mass spectrometer. Examination of the general dissociation behavior over a broad collision energy range shows that cobalt cluster cations dissociate exclusively by loss of single atoms (cluster ''evaporation''), with no evidence found for elimination of molecular cluster fragments. Bond dissociation energies for cobalt cluster cations, Co+n (n=2--18), are determined from measurements of the CID thresholds. Bond energies for neutral cobalt clusters, Con (n=4--18), are derived by combining these cationic bond energies with ionization energies for Con from the literature. The dependence of binding energy on cluster size is similar to that observed for iron clusters, and inspires some speculation regarding cluster ion structures

  19. Non-linear optical properties of gold quantum clusters. The smaller the better.

    Science.gov (United States)

    Russier-Antoine, Isabelle; Bertorelle, Franck; Vojkovic, Marin; Rayane, Driss; Salmon, Estelle; Jonin, Christian; Dugourd, Philippe; Antoine, Rodolphe; Brevet, Pierre-François

    2014-11-21

    By developing a new method for synthesizing atomically monodisperse Au15 nanoclusters stabilized with glutathione molecules and using the current state-of-the-art methods for synthesizing monodisperse protected Au25 nanoclusters, we investigated their nonlinear optical (NLO) properties after two-photon absorption. The two-photon emission spectra and the first hyperpolarizabilities of these particles were obtained using, in particular, a hyper-Rayleigh scattering technique. The influence on NLO of the excitation wavelength, the size as well as the nature of the ligands is also explored and discussed. Au15, the smallest stable thiolated gold nanocluster, presents remarkable nonlinear properties with respect to two-photon processes. The two-photon absorption cross-section at 780 nm for Au15 is ∼65,700 GM. This experimental cross-section value points to a quantum yield for two-photon emission of about 3 × 10(-7) at 475 nm for Au15. The first hyperpolarizability β for Au15 clusters (509 × 10(-30) esu), as compared to Au25 clusters (128 × 10(-30) esu), is larger considering the difference in the number of gold atoms. Also, 10(30) β per atom values reported for Au15 and Au25 clusters are more than two orders of magnitude larger than the values reported for Au NPs in the size range 10-50 nm, outlining the quantum cluster regime. PMID:25268982

  20. Interaction of small vacancy clusters with (1 1 4) twin-boundary in gold

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, Fayyaz [Department of Physics, The Islamia University of Bahawalpur, Bahawalpur 63120 (Pakistan); Hayat, Sardar Sikandar, E-mail: sikandariub@yahoo.co [Department of Physics and Astronomy, Hazara University, Mansehra 21300 (Pakistan); Imran, Muhammad [Department of Physics, The Islamia University of Bahawalpur, Bahawalpur 63120 (Pakistan)

    2011-03-01

    The molecular dynamics simulation technique with many-body and semi-empirical potentials is used to calculate the (1 1 4) twin-boundary in gold at different temperatures. Relaxations are found on both sides of the interface with the same magnitude and the phenomenon of coalescence is observed near the interface. The interactions of single-, di- and tri-vacancies with twin-interface at 300 K on mirror and off-mirror sites are calculated. Off-mirror arrangements are favorable for all vacancy clusters, except for the single-vacancy cluster, which is less repulsive on the mirror site. Vacancy clusters energetically prefer to lie at planes closest to the (1 1 4) interface rather than away from it. The effect of temperature on interaction behavior is also calculated.

  1. Electrical properties of thin YBa2Cu3O7-x films with embedded gold nano clusters

    International Nuclear Information System (INIS)

    High temperature superconducting devices such as magnetometers or gradiometers are usually made from a single thin film, although each part of the device needs to fulfill special requirements. These are for example a low flux noise in antenna structures and a low contact resistance to the bonding pads. These requirements can be achieved by embedding gold nano clusters in thin films of YBa2Cu3O7-x (YBCO), since they can act as flux pinning centers and they increase contact area to the film. We present studies on the formation of gold nano clusters during the pulsed laser deposition of thin YBCO films in dependence on the gold film thickness. We verified the high crystalline quality of the films by measuring Rocking curve widths. Size and distribution of the gold clusters were determined from AFM measurements. We compare the superconducting and noise properties of bridge structures and gradiometers with devices made of conventional YBCO films

  2. Elucidation of the Au-S bond in a passivated gold cluster through density functional theory calculations (abstract only)

    International Nuclear Information System (INIS)

    Gold clusters are of increasing interest due to a number of already established as well as new potential applications in different fields of nanotechnology. The use of gold nanoparticles can be significantly extended by surface modifications, sulfidation being the most popular. The identifications of preferred adsorption geometries, bond formation, and binding energies are helpful tools for understanding the properties of these particles. This study is focused on a 38-atom gold cluster passivated with 3-hydroxypropanthiolate linkers. Starting from the re-optimized global minimum structure of a bare 38-atom gold cluster (Doye and Wales 1998 New J. Chem. 22 733-44) and aiming at a description of the passivated particle, density functional theory calculations (within the framework of the Amsterdam density functional calculation package ADF 2006.01 (ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com)) were performed at the level of the generalized gradient approximation of Perdew and Wang from 1991, with triple-zeta Slater basis sets plus p- and f-polarization functions (TZ2P) for the 33 outermost electrons of each gold atom, and considering scalar relativistic effects. Using this methodology, the space around the gold cluster (with the distance of the S of the thiolate from the gold cluster surface in the range 2.3-2.6 A) was examined to identify the most favourable absorption site for the thiolate linker. As a result, a 3D map was created and low energy areas corresponding to the potentially most favourable site for one 3-hydroxypropanthiolate linker on the gold cluster localized. Structures representing these areas were further optimized and consequently analysed using Mulliken population analysis to compare charge distribution over the tested structures, Mayer bond order analysis, as well as electron localization function/indicator bond formation analysis. The results obtained will be presented in comparison

  3. Elucidation of the Au-S bond in a passivated gold cluster through density functional theory calculations (abstract only)

    Energy Technology Data Exchange (ETDEWEB)

    Sihelnikova, L; Tvaroska, I [Institute of Chemistry, Slovak Academy of Sciences, Bratislava (Slovakia)

    2008-02-13

    Gold clusters are of increasing interest due to a number of already established as well as new potential applications in different fields of nanotechnology. The use of gold nanoparticles can be significantly extended by surface modifications, sulfidation being the most popular. The identifications of preferred adsorption geometries, bond formation, and binding energies are helpful tools for understanding the properties of these particles. This study is focused on a 38-atom gold cluster passivated with 3-hydroxypropanthiolate linkers. Starting from the re-optimized global minimum structure of a bare 38-atom gold cluster (Doye and Wales 1998 New J. Chem. 22 733-44) and aiming at a description of the passivated particle, density functional theory calculations (within the framework of the Amsterdam density functional calculation package ADF 2006.01 (ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com)) were performed at the level of the generalized gradient approximation of Perdew and Wang from 1991, with triple-zeta Slater basis sets plus p- and f-polarization functions (TZ2P) for the 33 outermost electrons of each gold atom, and considering scalar relativistic effects. Using this methodology, the space around the gold cluster (with the distance of the S of the thiolate from the gold cluster surface in the range 2.3-2.6 A) was examined to identify the most favourable absorption site for the thiolate linker. As a result, a 3D map was created and low energy areas corresponding to the potentially most favourable site for one 3-hydroxypropanthiolate linker on the gold cluster localized. Structures representing these areas were further optimized and consequently analysed using Mulliken population analysis to compare charge distribution over the tested structures, Mayer bond order analysis, as well as electron localization function/indicator bond formation analysis. The results obtained will be presented in comparison

  4. Elucidation of the Au S bond in a passivated gold cluster through density functional theory calculations (abstract only)

    Science.gov (United States)

    Sihelniková, L.; Tvaroška, I.

    2008-02-01

    Gold clusters are of increasing interest due to a number of already established as well as new potential applications in different fields of nanotechnology. The use of gold nanoparticles can be significantly extended by surface modifications, sulfidation being the most popular. The identifications of preferred adsorption geometries, bond formation, and binding energies are helpful tools for understanding the properties of these particles. This study is focused on a 38-atom gold cluster passivated with 3-hydroxypropanthiolate linkers. Starting from the re-optimized global minimum structure of a bare 38-atom gold cluster (Doye and Wales 1998 New J. Chem. 22 733-44) and aiming at a description of the passivated particle, density functional theory calculations (within the framework of the Amsterdam density functional calculation package ADF 2006.01 (ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com)) were performed at the level of the generalized gradient approximation of Perdew and Wang from 1991, with triple-zeta Slater basis sets plus p- and f-polarization functions (TZ2P) for the 33 outermost electrons of each gold atom, and considering scalar relativistic effects. Using this methodology, the space around the gold cluster (with the distance of the S of the thiolate from the gold cluster surface in the range 2.3-2.6 Å) was examined to identify the most favourable absorption site for the thiolate linker. As a result, a 3D map was created and low energy areas corresponding to the potentially most favourable site for one 3-hydroxypropanthiolate linker on the gold cluster localized. Structures representing these areas were further optimized and consequently analysed using Mulliken population analysis to compare charge distribution over the tested structures, Mayer bond order analysis, as well as electron localization function/indicator bond formation analysis. The results obtained will be presented in comparison

  5. Elucidation of the Au-S bond in a passivated gold cluster through density functional theory calculations (abstract only).

    Science.gov (United States)

    Sihelniková, L; Tvaroška, I

    2008-02-13

    Gold clusters are of increasing interest due to a number of already established as well as new potential applications in different fields of nanotechnology. The use of gold nanoparticles can be significantly extended by surface modifications, sulfidation being the most popular. The identifications of preferred adsorption geometries, bond formation, and binding energies are helpful tools for understanding the properties of these particles. This study is focused on a 38-atom gold cluster passivated with 3-hydroxypropanthiolate linkers. Starting from the re-optimized global minimum structure of a bare 38-atom gold cluster (Doye and Wales 1998 New J. Chem. 22 733-44) and aiming at a description of the passivated particle, density functional theory calculations (within the framework of the Amsterdam density functional calculation package ADF 2006.01 (ADF2006.01, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com)) were performed at the level of the generalized gradient approximation of Perdew and Wang from 1991, with triple-zeta Slater basis sets plus p- and f-polarization functions (TZ2P) for the 33 outermost electrons of each gold atom, and considering scalar relativistic effects. Using this methodology, the space around the gold cluster (with the distance of the S of the thiolate from the gold cluster surface in the range 2.3-2.6 Å) was examined to identify the most favourable absorption site for the thiolate linker. As a result, a 3D map was created and low energy areas corresponding to the potentially most favourable site for one 3-hydroxypropanthiolate linker on the gold cluster localized. Structures representing these areas were further optimized and consequently analysed using Mulliken population analysis to compare charge distribution over the tested structures, Mayer bond order analysis, as well as electron localization function/indicator bond formation analysis. The results obtained will be presented in

  6. Luminescent quantum clusters of gold in transferrin family protein, lactoferrin exhibiting FRET

    Science.gov (United States)

    Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Verma, Pramod Kumar; Pal, Samir Kumar; Pradeep, Thalappil

    2010-12-01

    We report the synthesis of highly luminescent, water soluble quantum clusters (QCs) of gold, which are stabilized by an iron binding transferrin family protein, lactoferrin (Lf). The synthesized AuQC@Lfclusters were characterized using UV-Visiblespectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), photoluminescence (PL), matrix assisted laser desorption ionizationmass spectrometry (MALDI-MS), FTIR spectroscopy and circular dichroism (CD) spectroscopy along with picosecond-resolved lifetime measurements. Detailed investigations with FTIR and CD spectroscopy have revealed changes in the secondary structure of the protein in the cluster. We have also studied Förster resonance energy transfer (FRET) occurring between the protein and the cluster. The ability of the clusters to sense cupric ions selectively at ppm concentrations was tested. The stability of clusters in widely varying pH conditions and their continued luminescence make it feasible for them to be used for intracellular imaging and molecular delivery, particularly in view of Lf protection.We report the synthesis of highly luminescent, water soluble quantum clusters (QCs) of gold, which are stabilized by an iron binding transferrin family protein, lactoferrin (Lf). The synthesized AuQC@Lfclusters were characterized using UV-Visiblespectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), photoluminescence (PL), matrix assisted laser desorption ionizationmass spectrometry (MALDI-MS), FTIR spectroscopy and circular dichroism (CD) spectroscopy along with picosecond-resolved lifetime measurements. Detailed investigations with FTIR and CD spectroscopy have revealed changes in the secondary structure of the protein in the cluster. We have also studied Förster resonance energy transfer (FRET) occurring between the protein and the cluster. The ability of the clusters to sense cupric ions selectively at ppm concentrations was tested. The

  7. Cation-interlinking network cluster approach in application to extended defects in covalent-bonded glassy semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Shpotyuk, Oleh [Lviv Institute of Materials of SRC, Lviv (Ukraine); Institute of Physics, Jan Dlugosz University, Czestochowa (Poland); Boyko, Vitaliy [Lviv Institute of Materials of SRC, Lviv (Ukraine); Lviv Polytechnic National University (Ukraine); Hyla, Malgorzata [Institute of Physics, Jan Dlugosz University, Czestochowa (Poland)

    2009-08-15

    A principally new cation-interlinking network cluster approach (CINCA) was proposed to describe different types of glass-forming structural units in network covalent-bonded solids like to chalcogenide vitreous semiconductors. Within this approach, two (or three) interconnected cation-centered polyhedra form more stretched structural fragments conditionally named atomic clusters, reflecting in such a way whole backbone of covalent-bonded semiconductor multiply duplicated in a space. The probability of possible atomic clusters is estimated with numerical parameter giving average formation energy in respect to the number of atoms involved in the cluster and average coordination number. This approach was probed at the example of regular network clusters based on AsS{sub 3/2} pyramids mutually-interconnected through bridge -S- atom contrasted with irregular double-bond-based quasi-tetrahedral structural S=AsS{sub 3} defects within binary As-S system. The corresponding mathematical calculations confirming a preference of regularly-linked structural units over irregular ones was performed using HyperChem 7.5 program. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Hierarchy of bond stiffnesses within icosahedral-based gold clusters protected by thiolates

    Science.gov (United States)

    Yamazoe, Seiji; Takano, Shinjiro; Kurashige, Wataru; Yokoyama, Toshihiko; Nitta, Kiyofumi; Negishi, Yuichi; Tsukuda, Tatsuya

    2016-01-01

    Unique thermal properties of metal clusters are believed to originate from the hierarchy of the bonding. However, an atomic-level understanding of how the bond stiffnesses are affected by the atomic packing of a metal cluster and the interfacial structure with the surrounding environment has not been attained to date. Here we elucidate the hierarchy in the bond stiffness in thiolate-protected, icosahedral-based gold clusters Au25(SC2H4Ph)18, Au38(SC2H4Ph)24 and Au144(SC2H4Ph)60 by analysing Au L3-edge extended X-ray absorption fine structure data. The Au-Au bonds have different stiffnesses depending on their lengths. The long Au-Au bonds, which are more flexible than those in the bulk metal, are located at the icosahedral-based gold core surface. The short Au-Au bonds, which are stiffer than those in the bulk metal, are mainly distributed along the radial direction and form a cyclic structural backbone with the rigid Au-SR oligomers.

  9. Influence of the photothermal effect of a gold nanorod cluster on biofilm disinfection

    International Nuclear Information System (INIS)

    We evaluate a method for biofilm disinfection by raising biofilm temperature using the photothermal effect of a gold nanorod cluster. Gold nanorods (GNRs) are capable of generating enough heat to lyse bacteria by heating biofilm via laser irradiation. To test this, GNRs are synthesized using wet chemistry and a single GNR cluster is fabricated using photo-lithography technique. The GNR cluster is directly applied to the biofilm and its effects on bacteria are measured before and after laser irradiation. The photothermal effect of GNRs on the biofilm structure results in a considerable reduction of cell viability and biofilm thickness. Several quantitative measurements of bacterial mortality and biofilm destruction show an increase in efficacy with increasing durations of laser irradiation. Scanning electron microscopy images of the irradiated bacteria show obvious morphological damage such as rupture or collapse of the bacterial cell membrane in the biofilm. These results indicate that GNRs are useful and a potential material for use in photothermal treatments, particularly biofilm disinfection. (paper)

  10. In situ investigation of the mobility of small gold clusters on cleaved MgO surfaces

    Science.gov (United States)

    Metois, J. J.; Heinemann, K.; Poppa, H.

    1976-01-01

    The mobility of small clusters of gold (about 10 A in diameter) on electron-beam-cleaved MgO surfaces was studied by in situ transmission electron microscopy under controlled vacuum and temperature conditions. During the first 10 min following a deposition at room temperature, over 10 per cent of the crystallites moved over short distances (about 20 A) discontinuously, with a velocity greater than 150 A/sec. Eighty per cent of the mobility events were characterized by the avoidance of proximity of other crystallites, and this was tentatively explained as the result of repulsive elastic forces between the interacting crystallites.

  11. Dissociation energies of gold clusters AuN+, N=7-27

    International Nuclear Information System (INIS)

    Unimolecular decay rates and monomer-dimer branching ratios of gold clusters AuN+ (N=7-27) have been measured as a function of excitation energy in photodissociation experiments on size-selected clusters stored in a Penning trap. Part of the data set has previously been used to extract model-free values of dissociation energies [Vogel et al., Phys. Rev. Lett. 87, 013401 (2001)]. Other parts of the data set do not allow this analysis. We use these data to extract tentative dissociation energies, based on the systematics of deviations between an Arrhenius analysis and the model-free values. The observed systematics also allows an estimate of the true frequency factor which often is much higher than the Arrhenius value but in good agreement with the expected detailed balance value. The data are also reanalyzed including radiative cooling which may explain part of the discrepancy between model-free and Arrhenius dissociation-energy values

  12. Au(n)Hg(m) clusters: mercury aurides, gold amalgams, or van der Waals aggregates?

    Science.gov (United States)

    Zaleski-Ejgierd, Patryk; Pyykkö, Pekka

    2009-11-12

    The class of bimetallic clusters, Au(n)M(m) (M = Zn, Cd, Hg), is calculated at the ab initio level using the DFT, RI-MP2, and CCSD(T) methods. For the triatomic Au2M (M = Zn, Cd), the auride-type linear Au-M-Au structures are preferred; for Au2Hg, the linear Au-Au-Hg "amalgam" is preferred. The mixed cation [HgAuHg]+, an analog of the known solid-state species Hg32+, is predicted. For larger Au(n)Hg(m) clusters, the results are similar to the isoelectronic Au(n)M- anions. Several local minima and transition states are identified. All are found to be planar. PMID:19228004

  13. AunHgm Clusters: Mercury Aurides, Gold Amalgams, or van der Waals Aggregates?

    Science.gov (United States)

    Zaleski-Ejgierd, Patryk; Pyykkö, Pekka

    2009-02-01

    The class of bimetallic clusters, AunMm (M = Zn, Cd, Hg), is calculated at the ab initio level using the DFT, RI-MP2, and CCSD(T) methods. For the triatomic Au2M (M = Zn, Cd), the auride-type linear Au-M-Au structures are preferred; for Au2Hg, the linear Au-Au-Hg "amalgam" is preferred. The mixed cation [HgAuHg]+, an analog of the known solid-state species Hg32+, is predicted. For larger AunHgm clusters, the results are similar to the isoelectronic AunM- anions. Several local minima and transition states are identified. All are found to be planar.

  14. Stable compositions and geometrical structures of titanium oxide cluster cations and anions studied by ion mobility mass spectrometry

    Science.gov (United States)

    Ohshimo, Keijiro; Norimasa, Naoya; Moriyama, Ryoichi; Misaizu, Fuminori

    2016-05-01

    Geometrical structures of titanium oxide cluster cations and anions have been investigated by ion mobility mass spectrometry and quantum chemical calculations based on density functional theory. Stable cluster compositions with respect to collision induced dissociation were also determined by changing ion injection energy to an ion drift cell for mobility measurements. The TinO2n-1+ cations and TinO2n- anions were predominantly observed at high injection energies, in addition to TinO2n+ for cations and TinO2n+1- for anions. Collision cross sections of TinO2n+ and TinO2n+1- for n = 1-7, determined by ion mobility mass spectrometry, were compared with those obtained theoretically as orientation-averaged cross sections for the optimized structures by quantum chemical calculations. All of the geometrical structures thus assigned have three-dimensional structures, which are in marked contrast with other oxides of late transition metals. One-oxygen atom dissociation processes from TinO2n+ and TinO2n+1- by collisions were also explained by analysis of spin density distributions.

  15. Design, Synthesis, and Characterization of Novel Thiol-Derivatized Ibuprofen Monolayer Protected Gold Clusters

    International Nuclear Information System (INIS)

    A series of new thiol-derivatized ibuprofen monolayer protected gold clusters have been prepared by amidation of ibuprofen with alkyl alcohol or aminophenol affording the carboxamide, N-hydroxyalkyl amide 2, and N-hydroxyphenyl amide 6, which were then tosylate with p-toluenesulfonyl chloride at hydroxyl group to give 3 and 7. Reactions of 3 and 7 with NaSH afforded the mercapto derivatives 4 and 8. Conducting Brust’s reaction with a 3:1 mole ratio of thiolate ibuprofen/ AuCl4- yielded polydisperse thiol-derivatized ibuprofen-MPCs 5 and 9. All compounds have been identified by NMR, MS, UV, and IR spectroscopies. Compounds 4 and 8 and the MPCs 5 and 9 have been investigated by using the method of 1H NMR spectroscopy. The broadening of the signals from 0.8 to 2.0 ppm in 1H NMR spectrum of MPCs 5 and 9 confirmed the success of the conjugation of thiol-containing derivatives with nano gold cluster.

  16. Adsorptive and stripping behavior of methylene blue at gold electrodes in the presence of cationic gemini surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jiangwen; Zhao, Faqiong; Zhao, Jia; Zeng, Baizhao [Wuhan University, Wuhan (China). Department of Chemistry

    2005-10-10

    The adsorptive and stripping behavior of methylene blue (i.e. methylene blue chloride, MB) at a gold electrode has been studied with voltammetry, alternating current impedance spectra (ACIS) and quartz crystal microbalance (QCM). MB exhibits a pair of cyclic voltammetry peaks at about -0.3 V (versus SCE) in 0.05 M pH 6.9 phosphate buffer solutions. In the presence of cationic gemini surfactants such as C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 4}H{sub 8}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 4}-C{sub 16}), C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 4}H{sub 7}OH-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 4}OH-C{sub 16}), C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-CH{sub 2}-C{sub 6}H{sub 4}-CH{sub 2}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-ph-C{sub 16}) and C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 12}H{sub 24}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 12}-C{sub 16}), the anodic peak grows rapidly and moves in positive direction, but the cathodic peak gradually decreases, due to the association adsorption and electrostatic interaction of the geminis with MB and its reduced product (i.e. leuko methylene blue, LMB). With the aid of geminis the adsorption amount of MB increases under open-circuit, but the impedance of the mixed adsorption film to Fe(CN){sub 6}{sup 3-/4-} almost keeps unchanged, compared with either bare gold electrodes or MB film, while the adsorption film of geminis exhibits greater impedance. This probably is due to the electron medium action of MB in the film. Gemini surfactants with same alkyl-chain (i.e. -(CH{sub 2}){sub 15}CH{sub 3}) but different molecular structure, exhibit different influence. The enhancing action of geminis studied follows such order as: C{sub 16}-ph-C{sub 16} > C{sub 16}-C{sub 4}-C{sub 16} > C{sub 16}-C{sub 4}OH-C{sub 16} > C{sub 16}-C{sub 12}-C{sub 16}. The change of peak potential was ascribed to the interaction between MB and surfactants

  17. Adsorptive and stripping behavior of methylene blue at gold electrodes in the presence of cationic gemini surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Li Jiangwen [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Zhao Faqiong [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Zhao Jia [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Zeng Baizhao [Department of Chemistry, Wuhan University, Wuhan 430072 (China)]. E-mail: zengbz@chem.whu.edu.cn

    2005-10-10

    The adsorptive and stripping behavior of methylene blue (i.e. methylene blue chloride, MB) at a gold electrode has been studied with voltammetry, alternating current impedance spectra (ACIS) and quartz crystal microbalance (QCM). MB exhibits a pair of cyclic voltammetry peaks at about -0.3 V (versus SCE) in 0.05 M pH 6.9 phosphate buffer solutions. In the presence of cationic gemini surfactants such as C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 4}H{sub 8}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 4}-C{sub 16}), C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 4}H{sub 7}OH-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 4}OH-C{sub 16}), C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-CH{sub 2}-C{sub 6}H{sub 4}-CH{sub 2}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-ph-C{sub 16}) and C{sub 16}H{sub 33}N(CH{sub 3}){sub 2}-C{sub 12}H{sub 24}-N(CH{sub 3}){sub 2}C{sub 16}H{sub 33}Br{sub 2} (C{sub 16}-C{sub 12}-C{sub 16}), the anodic peak grows rapidly and moves in positive direction, but the cathodic peak gradually decreases, due to the association adsorption and electrostatic interaction of the geminis with MB and its reduced product (i.e. leuko methylene blue, LMB). With the aid of geminis the adsorption amount of MB increases under open-circuit, but the impedance of the mixed adsorption film to Fe(CN){sub 6} {sup 3-/4-} almost keeps unchanged, compared with either bare gold electrodes or MB film, while the adsorption film of geminis exhibits greater impedance. This probably is due to the electron medium action of MB in the film. Gemini surfactants with same alkyl-chain (i.e. -(CH{sub 2}){sub 15}CH{sub 3}) but different molecular structure, exhibit different influence. The enhancing action of geminis studied follows such order as: C{sub 16}-ph-C{sub 16} > C{sub 16}-C{sub 4}-C{sub 16} > C{sub 16}-C{sub 4}OH-C{sub 16} > C{sub 16}-C{sub 12}-C{sub 16}. The change of peak potential was ascribed to the interaction between MB and

  18. Theoretical design of a novel copper doped gold cluster supported on graphene utilizing ab initio molecular dynamics simulations

    International Nuclear Information System (INIS)

    Ab initio molecular dynamics simulations have been used to inspect the adsorption of O2 to a small gold-copper alloy cluster supported on graphene. The exposed Cu atom in this cluster acts as a crucial attractive site for the approaching of O2 and consequently widens the reaction channel for the adsorption process. Conversely, a pure Au cluster on the same graphene support is inactive for the O2 adsorption because the corresponding reaction channel for the adsorption is very narrow. These results clearly indicate that doping a different metal to the Au cluster is a way to enhance the oxygen adsorption and to promote catalytic reactions

  19. Photon to thermal response of a single patterned gold nanorod cluster under near-infrared laser irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Wonjin; Kim, Min Jun [Department of Mechanical Engineering and Mechanics, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States); Freedman, Kevin; Bose, Ranjita K; Lau, Kenneth K S [Department of Chemical and Biological Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States); Yi, Dong Kee [Gachon BioNano Research Institute, Kyungwon University, Sungnam 461-701 (Korea, Republic of); Solomon, Sally D, E-mail: mkim@coe.drexel.edu [Department of Chemistry, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States)

    2011-03-15

    The potential applications of the photon to thermal conversion technique by gold nanorods has attracted attention for biomedical applications since they show an intense absorption spectrum in the near-infrared region, and therefore, penetrate more deeply into biological tissues. The goal in this study is to assess a local heating phenomenon with a single patterned cluster of gold nanorods that are prepared as a wet chemically synthesized gold nanorod solution and mixed with aqueous 1% alginate and 0.1 M calcium chloride. In particular, we utilized the initiated chemical vapor deposition method to coat the cluster with poly(2-hydroxyethyl methacrylate) to enhance its high temperature resistance in the solution. The influence of the thermal energy on the surroundings is studied by measuring the surface temperature of the single patterned gold nanorod cluster as a function of laser irradiation time. The experimental results were compared with numerical simulation results. The results showed that the irradiated gold nanorods could rapidly heat to maximum surface temperatures of over 60 {sup 0}C within 120 s. Furthermore, the temperature remained almost constant (i.e. reached a steady state) under continuous laser irradiation and rapidly cooled to the initial temperature within 90 s when the laser was turned off.

  20. Gold/Iron Carbonyl Clusters for Tailored Au/FeOx Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Stefania Albonetti

    2011-12-01

    Full Text Available A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO16] and [NEt4][AuFe4(CO16] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H2 (PROX as model reactions. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions.

  1. Global minimization of gold clusters by combining neural network potentials and the basin-hopping method

    Science.gov (United States)

    Ouyang, Runhai; Xie, Yu; Jiang, De-En

    2015-09-01

    Neural network potentials trained by first-principles density functional theory total energies were applied to search for global minima of gold nanoclusters within the basin-hopping method. Using Au58 as an example, we found a new putative global minimum which has a core-shell structure of Au10@Au48 and C4 symmetry. This new structure of Au58 is 0.24 eV per formula more stable than the best previous model that has C1 symmetry. This work demonstrates that neural network potentials combined with the basin-hopping method could be very useful in global minimization for medium-sized metal clusters which might be computationally prohibitive for first principles density functional theory.Neural network potentials trained by first-principles density functional theory total energies were applied to search for global minima of gold nanoclusters within the basin-hopping method. Using Au58 as an example, we found a new putative global minimum which has a core-shell structure of Au10@Au48 and C4 symmetry. This new structure of Au58 is 0.24 eV per formula more stable than the best previous model that has C1 symmetry. This work demonstrates that neural network potentials combined with the basin-hopping method could be very useful in global minimization for medium-sized metal clusters which might be computationally prohibitive for first principles density functional theory. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03903g

  2. Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping.

    Science.gov (United States)

    Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

    2016-04-18

    The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping. PMID:26714587

  3. Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Nir; Browning, Nigel D.

    2011-06-16

    Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

  4. Design, Synthesis, and Characterization of Novel Thiol-Derivatized Ibuprofen Monolayer Protected Gold Clusters

    Directory of Open Access Journals (Sweden)

    Kuan-Han Lee

    2013-01-01

    Full Text Available A series of new thiol-derivatized ibuprofen monolayer protected gold clusters have been prepared by amidation of ibuprofen with alkyl alcohol or aminophenol affording the carboxamides, N-hydroxyalkyl amide 2, and N-hydroxyphenyl amide 6, which were then tosylated with p-toluenesulfonyl chloride at hydroxyl group to give 3 and 7. Reactions of 3 and 7 with NaSH afforded the mercapto derivatives 4 and 8. Conducting Brust’s reaction with a 3 : 1 mole ratio of thiolate ibuprofen/AuCl4- yielded polydisperse thiol-derivatized ibuprofen-MPCs 5 and 9. All compounds have been identified by NMR, MS, UV, and IR spectroscopies. Compounds 4 and 8 and the MPCs 5 and 9 have been investigated by using the method of 1H NMR spectroscopy. The broadening of the signals from 0.8 to 2.0 ppm in 1H NMR spectrum of MPCs 5 and 9 confirmed the success of the conjugation of thiol-containing derivatives with nanogold cluster.

  5. Plasmonic Non-linear Conversion of Continuous Wave Light by Gold Nanoparticle Clusters withFluorescent Protein Loaded Gaps

    CERN Document Server

    Salakhutdinov, Ildar; Abak, Musa Kurtulus; Turkpence, Deniz; Piantanida, Luca; Fruk, Ljiljana; Tasgin, Mehmet Emre; Lazzarino, Marco; Bek, Alpan

    2014-01-01

    We propose and demonstrate a method which is feasible for deterministic activation of few molecules. Our method relies on non-linear optical excitation of few enhanced yellow fluorescent protein molecules that are sandwiched between gaps of asymmetrically constructed plasmonic gold nanoparticle clusters. We observe that as infrared photons, which cannot get absorbed by fluorescent molecules, are converted through efficient second harmonic generation activity of gold nanoparticles to visible photons, the molecules absorb them and fluoresce. Our numerical simulations demonstrate that observation of SHG with cw laser becomes possible owing to the cooperative action of conversion enhancement through Fano resonance, hybridization in the plasmon absorption spectrum and the size asymmetry of nanoparticle dimers.

  6. A cationic copper(I) iodide cluster MOF exhibiting unusual ligand assisted thermochromism.

    Science.gov (United States)

    Yadav, Ashok; Srivastava, Anant Kumar; Balamurugan, Ayyakkalai; Boomishankar, Ramamoorthy

    2014-06-14

    By employing a tridentate thiophosphoramide ligand, [(NHAQ)3P[double bond, length as m-dash]S] (AQ = 3-quinolinyl), a cationic MOF, {[Cu6I5(L(1))2](OH)·3DMF·2.5MeOH}n, was synthesized. Photo-physical studies on the 2D-MOF showed an unusual thermochromic behaviour emitting a blue fluorescence at 298 K due to the AQ chromophore and an orange-yellow phosphorescence at 77 K due to the [Cu6I5](+) unit. PMID:24760039

  7. Ultrafast photoinduced enhancement of nonlinear optical response in 15-atom gold clusters on indium tin oxide conducting film.

    Science.gov (United States)

    Kumar, Sunil; Shibu, E S; Pradeep, T; Sood, A K

    2013-04-01

    We show that the third order optical nonlinearity of 15-atom gold clusters is significantly enhanced when in contact with indium tin oxide (ITO) conducting film. Open and close aperture z-scan experiments together with non-degenerate pump-probe differential transmission experiments were done using 80 fs laser pulses centered at 395 nm and 790 nm on gold clusters encased inside cyclodextrin cavities. We show that two photon absorption coefficient is enhanced by an order of magnitude as compared to that when the clusters are on pristine glass plate. The enhancement for the nonlinear optical refraction coefficient is ~3 times. The photo-induced excited state absorption using pump-probe experiments at pump wavelength of 395 nm and probe at 790 nm also show an enhancement by an order of magnitude. These results attributed to the excited state energy transfer in the coupled gold cluster-ITO system are different from the enhancement seen so far in charge donor-acceptor complexes and nanoparticle-conjugate polymer composites. PMID:23571938

  8. Photoelectron spectroscopy of boron-gold alloy clusters and boron boronyl clusters: B3Au(n)(-) and B3(BO)n(-) (n = 1, 2).

    Science.gov (United States)

    Chen, Qiang; Bai, Hui; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2013-07-28

    Photoelectron spectroscopy and density-functional theory are combined to study the structures and chemical bonding in boron-gold alloy clusters and boron boronyl clusters: B3Au(n)(-) and B3(BO)n(-) (n = 1, 2). Vibrationally resolved photoelectron spectra are obtained for all four species and the B-Au and B-BO clusters exhibit similar spectral patterns, with the latter species having higher electron binding energies. The electron affinities of B3Au, B3Au2, B3(BO), and B3(BO)2 are determined to be 2.29 ± 0.02, 3.17 ± 0.03, 2.71 ± 0.02, and 4.44 ± 0.02 eV, respectively. The anion and neutral clusters turn out to be isostructural and isovalent to the B3H(n)(-)∕B3H(n) (n = 1, 2) species, which are similar in bonding owing to the fact that Au, BO, and H are monovalent σ ligands. All B3Au(n)(-) and B3(BO)n(-) (n = 1, 2) clusters are aromatic with 2π electrons. The current results provide new examples for the Au∕H and BO∕H isolobal analogy and enrich the chemistry of boronyl and gold. PMID:23901981

  9. Theoretical design of a novel copper doped gold cluster supported on graphene utilizing ab initio molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Koizumi, Kenichi; Nobusada, Katsuyuki [Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki 444-8585 (Japan); Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520 (Japan); Boero, Mauro [Institut de Physique et Chimie des Matériaux de Strasbourg UMR 7504, University of Strasbourg and CNRS, 23 rue du Loess, F-67034 Strasbourg (France)

    2015-12-31

    Ab initio molecular dynamics simulations have been used to inspect the adsorption of O{sub 2} to a small gold-copper alloy cluster supported on graphene. The exposed Cu atom in this cluster acts as a crucial attractive site for the approaching of O{sub 2} and consequently widens the reaction channel for the adsorption process. Conversely, a pure Au cluster on the same graphene support is inactive for the O{sub 2} adsorption because the corresponding reaction channel for the adsorption is very narrow. These results clearly indicate that doping a different metal to the Au cluster is a way to enhance the oxygen adsorption and to promote catalytic reactions.

  10. Large clusters of gold deposits and large-scale metallogene-sis in the Jiaodong Peninsula, Eastern China

    Institute of Scientific and Technical Information of China (English)

    ZHAI; Mingguo

    2001-01-01

    Peninsula (in Chinese), Beijing: Seismology Press, 1994, 1-56.[21]Luo, W. C., Wu, Q. S., Dating of the mineralizing age of gold deposits in Jiaodong Peninsula using the alteration minerals, Chinese Science Bulletin (in Chinese), 1987, 32 (16): 1245-1248.[22]Farmer, G. L., DePaolo, D. J., Nd and Sr isotope study of hydrothermally altered granites at San Manud, Arizona: Impli-cations for element migration paths during formation of porphyry copper ore deposits, Economic Geology, 1987, 82: 1142-1151.[23]Qiu, H. N., Peng, L., Chronology of 40Ar/39Ar and Dating of Fluid Inclusions (in Chinese), Hefei: University of Science and Technology of China Press, 1997, 206-223.[24]Yang, J. H., Zhou, X. H., Rb-Sr, Sm-Nd, and Pb isotope systematics of pyrites: Implications for the age and genesis of lode deposits, Geology, 2001 (in press).[25]Chen, G. Y., Shao, W., Sun, D., Genetic Mineralogy of Gold Deposits in Jiaodong Region with Emphasis on Gold Pros-pecting (in Chinese), Chongqing: Chongqing Publishing House, 1989: 1-452.[26]Lüders, V., Ziemann, M., Possibilities and limits of infrared light microthermometry applied to studies of pyrite-hosted fluid inclusions, Chemical Geology, 1999, 154(1-4): 169-178.[27]Yang, J. H., Ma, H. M., Zhou, X. H. et al., Genesis and significance of component zones in pyrites from Penglai gold de-posit, Shandong Province, Scientia Geologica Sinica (in Chinese), 2000, 35(2): 168-174.[28]Guan, K., Luo, Z. K., Miao, L. C. et al., SHRIMP in zircon chronology for Guojialing suite granite in Jiaodong district, Scientia Geologica Sinica (in Chinese), 1998, 33: 318-328.[29]Wang, L. G., Qiu, Y. M., McNaughton, N. J. et al., Constraints on crustal evolution and gold metallogeny in the North-western Jiaodong Peninsula,China,from SHRIMP U-Pb zircon studies of granitoids, Ore Geology Reviews, 1998, 13: 275-291.[30]Yang, J. H., Age and metallogenic dynamics of gold mineralization in Jiaodong Peninsula, eastern

  11. Accurate ionization potential of gold anionic clusters from density functional theory and many-body perturbation theory

    CERN Document Server

    Tanwar, A; Trevisanutto, P E; Chiodo, L; Della Sala, F; 10.1140/epjb/e2013-40016-5

    2013-01-01

    We present a theoretical study of the ionization potential in small anionic gold clusters, using density functional theory, with and without exact-exchange, and many body perturbation theory, namely the G0W0 approach. We find that G0W0 is the best approach and correctly describes the first ionization potential with an accuracy of about 0.1 eV.

  12. Probing the Structures and Electronic Properties of Dual-Phosphorus-Doped Gold Cluster Anions (AunP-2, n = 1–8): A Density functional Theory Investigation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Kang-Ming; Huang, Teng; Liu, Yi-Rong; Jiang, Shuai; Zhang, Yang; Lv, Yu-Zhou; Gai, Yan-Bo; Huang, Wei

    2015-07-29

    The geometries of gold clusters doped with two phosphorus atoms, (AunP-2, n = 1–8) were investigated using density functional theory (DFT) methods. Various two-dimensional (2D) and three-dimensional (3D) structures of the doped clusters were studied. The results indicate that the structures of dual-phosphorus-doped gold clusters exhibit large differences from those of pure gold clusters with small cluster sizes. In our study, as for Au6P-2, two cis–trans isomers were found. The global minimum of Au8P-2 presents a similar configuration to that of Au-20, a pyramid-shaped unit, and the potential novel optical and catalytic properties of this structure warrant further attention. The higher stability of AunP-2 clusters relative to Au-n+2 (n = 1–8) clusters was verified based on various energy parameters, and the results indicate that the phosphorus atom can improve the stabilities of the gold clusters. We then explored the evolutionary path of (n = 1–8) clusters. We found that AunP-2 clusters exhibit the 2D–3D structural transition at n = 6, which is much clearer and faster than that of pure gold clusters and single-phosphorus-doped clusters. The electronic properties of AunP-2 (n = 1–8) were then investigated. The photoelectron spectra provide additional fundamental information on the structures and molecular orbitals shed light on the evolution of AunP-2 (n = 1–8). Natural bond orbital (NBO) described the charge distribution in stabilizing structures and revealed the strong relativistic effects of the gold atoms.

  13. Fine-tuned h-ferritin nanocage with multiple gold clusters as near-infrared kidney specific targeting nanoprobe.

    Science.gov (United States)

    Sun, Cuiji; Yuan, Yi; Xu, Zhonghe; Ji, Tianjiao; Tian, Yanhua; Wu, Shan; Lei, Jianlin; Li, Jingyuan; Gao, Ning; Nie, Guangjun

    2015-02-18

    When stabilized and functionalized by biomolecules, noble metal (such as gold and silver) cluster-based hybrid nanocomposites have shown great promise for biomedical applications, due to their unique physiochemical properties originating from the inorganic elements and specific functionality and biocompatibility from their biological components. Although certain promise for bioimaging, biosensing, and biomimetic catalysis has been demonstrated, it is still a great challenge to integrate the defined functionality of the biomolecules with enhanced or novel physiochemical properties of the metal clusters, under control at the molecular level. Herein, based on molecular dynamics simulation of a gold (Au) cluster assembly, we designed near-infrared (NIR) fluorescent hybrid nanocomposites with multiple Au clusters within an apo H-ferritin (HFt) nanocage. The fluorescence quantum yield of near-infrared (NIR) Au-HFt is about 63.4% and the emission peak is 810 nm. The NIR Au-HFt is one of the first native protein-guided Au cluster-based nanomaterials for in vivo biowindow imaging. In vivo fluorescent imaging and quantification of Au element confirmed that Au-HFt not only retained the kidney targeting properties of HFt well (about 10 times higher Au concentration in kidney than in liver and spleen, the most common organs for nanoparticle accumulation), but also gained strong NIR imaging capability for live animals. The NIR Au-HFt showed powerful tissue penetrating ability, strong fluorescent efficiency, and excellent kidney targeting specificity. These results thus open new opportunities for kidney disease imaging and theranostic applications. PMID:25594844

  14. Theoretical study of structural and optical properties of small silver and gold clusters at defect centers of MgO

    Energy Technology Data Exchange (ETDEWEB)

    Buergel, Christian; Bonacic-Koutecky, Vlasta [Department of Chemistry, Humboldt-Universitaet zu Berlin (Germany); Mitric, Roland [Fachbereich Physik, Freie Universitaet Berlin (Germany)

    2010-05-15

    In this contribution we present the structural and optical properties of small noble-metal clusters at the F{sub S}-center defect of the MgO (100) support. We focus on comparing absorption and emission properties of supported silver and gold clusters. It will be shown that the leading absorption features in the low energy regime are similar for supported silver and gold clusters of the same size, in spite of the direct involvement of d electrons from Au atoms due to strong relativistic effects. Molecular dynamics (MD) simulations in the excited electronic states allow us to unravel relaxation mechanism and to propose the smallest noble-metal clusters at the F{sub S}-center defect, Ag{sub 2,4} rate at F{sub 5c} and Au{sub 2,4} rate at F{sub 5c}, as good candidates for emissive centers. In contrast, larger supported Ag{sub 8} rate at {sub 5c} and Au{sub 8} rate at F{sub 5c} clusters are unlikely to fluoresce. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  15. Tuning of localized surface plasmon enhanced optical responses of gold nanoparticles/cationic polythiophene and its application to SERS

    Czech Academy of Sciences Publication Activity Database

    Kazim, Samrana; Pfleger, Jiří; Procházka, M.; Bondarev, M.; Vohlídal, J.

    Dresden : Leibniz-Institut für Polymerforschung Dresden e. V, 2012. s. 41. [IPF Colloquium Functional Polymers and Composites for Applications in Organic Electronics and Sensorics /10./. 07.11.2012-08.11.2012, Dresden] R&D Projects: GA ČR GAP108/12/1143; GA MŠk 7E10040 EU Projects: European Commission(XE) 247745 - FlexNet Institutional support: RVO:61389013 Keywords : gold nanoparticles * SERS Subject RIV: CD - Macromolecular Chemistry

  16. Impedance spectroscopic investigation of the effect of thin azo-calix[4]arene film type on the cation sensitivity of the gold electrodes

    International Nuclear Information System (INIS)

    In this work, we report the impedance spectroscopic investigation of the effect of the thin film type on the selectivity of gold/azo-calix[4]arene electrodes. For this purpose, two C1 and C3 azo-calix[4]arene derivative molecules, used as thin films, are deposited by spin-coating process on the gold surface. These thin films were first studied using contact angle measurements. This revealed a less hydrophobic character for C3 thin film, which has been attributed to the presence of hydroxyl groups at the lower rim. The sensitivity study, by Electrochemical Impedance Spectroscopy (EIS), towards Cu2+ and Eu3+ cations, has showed that the C3 thin film is more sensitive and selective towards Eu3+ than C1. This best performance is due to the presence of two ester groups acting as clips and leading to more complexation stability. The EIS results were modeled by an appropriate equivalent circuit for the aim of elucidating electrical properties of thin films. This modeling has exposed that C3 thin film presents lower ionic conductivity and limited diffusion phenomenon at the interface. Highlights: → C1 and C3 azo-calix[4]arenes thin films are deposited on the gold surface. → The lower hydrophobicity for C3 was attributed to the presence of hydroxyl groups. → The C3 thin film is more sensitive and selective towards Eu3+ than C1 one. → This best performance is due to the presence of two ester groups acting as clips.

  17. Crystal structure and solid-state properties of discrete hexa cationic trinuclear zinc triazole cluster

    Indian Academy of Sciences (India)

    Chatla Naga Babu; Paladugu Suresh; Arruri Sathyanarayana; Prasenjit Das; Ganesan Prabusankar

    2015-08-01

    A linear trinuclear cluster of the type [{Zn3 (HTrz)6 (H2O)6}6+ (NO$_{3}^{−}$)6 (H2O)] (ZnT) has been synthesized by one-pot reaction between 1,2,4-triazole and Zn(NO3).6H2O. Molecule consists of three Zn2+ ions linearly connected by 1,2,4-triazole with tri-fold symmetry. The coordination geometry around the zinc centre is octahedral with zinc-zinc separation of 3.810 Å. The coordination environment of central Zn2+ ion is satisfied by nitrogen atoms of six 1,2,4-triazoles, while the geometry of terminal Zn2+ ions is fulfilled by nitrogen atoms of three 1,2,4-triazoles and three water molecules. The thermal and absorption properties of ZnT have been reported for the first time.

  18. Emergence of large chiroptical responses by ligand exchange cross-linking of monolayer-protected gold clusters with chiral dithiol.

    Science.gov (United States)

    Yao, Hiroshi; Yaomura, Shota

    2013-05-28

    We here present a study of cross-linking chemistry of optically inactive monothiol-protected gold clusters by chiral bidentate dithiol with two stereogenic centers, (2R,3R)-1,4-dimercapto-2,3-butanediol (L-dithiothreitol; L-DTT), and explore the impacts of the cross-linking on their chiroptical responses. The pristine protective ligand is racemic penicillamine (rac-Pen), and the products of the ligand exchange reactions include clusters containing both rac-Pen and L-DTT (partial exchange). Electrophoresis using polyacrylamide gel with a very low gel concentration (3%) can make the products separable into two components, each of which has the similar mean core diameter of 0.78 and 0.83 nm, so the difference in the relative mobility is mainly ascribed to the size of the cluster assembly. In addition, very large optical activity with the maximum anisotropy factors of about 1.0 × 10(-3) is found for the assemblies. In comparison with chiral 1,3-dithiol protection incapable of cross-linking between gold clusters, we propose that the observed optical activity is due to surface intrinsic handedness caused by a cyclic cross-linking with at least two L-DTT molecules. PMID:23635318

  19. Probing the structures of gold-aluminum alloy clusters AuxAly(-): a joint experimental and theoretical study.

    Science.gov (United States)

    Khetrapal, Navneet Singh; Jian, Tian; Pal, Rhitankar; Lopez, Gary V; Pande, Seema; Wang, Lai-Sheng; Zeng, Xiao Cheng

    2016-05-01

    Besides the size and structure, compositions can also dramatically affect the properties of alloy nanoclusters. Due to the added degrees of freedom, determination of the global minimum structures for multi-component nanoclusters poses even greater challenges, both experimentally and theoretically. Here we report a systematic and joint experimental/theoretical study of a series of gold-aluminum alloy clusters, AuxAly(-) (x + y = 7,8), with various compositions (x = 1-3; y = 4-7). Well-resolved photoelectron spectra have been obtained for these clusters at different photon energies. Basin-hopping global searches, coupled with density functional theory calculations, are used to identify low-lying structures of the bimetallic clusters. By comparing computed electronic densities of states of the low-lying isomers with the experimental photoelectron spectra, the global minima are determined. It is found that for y ≥ 6 there is a strong tendency to form the magic-number square bi-pyramid motif of Al6(-) in the AuxAly(-) clusters, suggesting that the Al-Al interaction dominates the Au-Au interaction in the mixed clusters. A closely related trend is that for x > 1, the gold atoms tend to be separated by Al atoms unless only the magic-number Al6(-) square bi-pyramid motif is present, suggesting that in the small-sized mixed clusters, Al and Au components do not completely mix with one another. Overall, the Al component appears to play a more dominant role due to the high robustness of the magic-number Al6(-) square bi-pyramid motif, whereas the Au component tends to be either "adsorbed" onto the Al6(-) square bi-pyramid motif if y ≥ 6, or stays away from one another if x < y < 6. PMID:27119726

  20. Three Alkali-Metal-Gold-Gallium Systems. Ternary Tunnel Structures and Some Problems with Poorly Ordered Cations

    Energy Technology Data Exchange (ETDEWEB)

    Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.

    2012-06-27

    Six new intermetallic compounds have been characterized in the alkali metal (A = Na, Rb, Cs)–gold–gallium systems. Three isostructural compounds with the general composition A0.55Au2Ga2, two others of AAu3Ga2 (A = Rb, Cs), and the related Na13Au41.2Ga30.3 were synthesized via typical high-temperature reactions and their crystal structures determined by single-crystal X-ray diffraction analysis: Na0.56(9)Au2Ga2 (I, I4/mcm, a = 8.718(1) Å, c = 4.857(1) Å, Z = 4), Rb0.56(1)Au2Ga2 (II, I4/mcm, a = 8.950(1) Å, c = 4.829(1) Å, Z = 4), Cs0.54(2)Au2Ga2 (III, I4/mcm, a = 9.077(1) Å, c = 4.815(1) Å, Z = 4), RbAu3Ga2 (IV, Pnma, a = 13.384(3) Å, b = 5.577(1) Å, c = 7.017(1) Å, Z = 4), CsAu3Ga2 (V, Pnma, a = 13.511(3) Å, b = 5.614(2) Å, c = 7.146(1) Å, Z = 4), Na13Au41.2(1)Ga30.3(1) (VI, P6 mmm, a = 19.550(3) Å, c = 8.990(2) Å, Z = 2). The first three compounds (I–III) are isostructural with tetragonal K0.55Au2Ga2 and likewise contain planar eight-member Au/Ga rings that stack along c to generate tunnels and that contain varying degrees of disordered Na–Cs cations. The cation dispositions are much more clearly and reasonably defined by electron density mapping than through least-squares refinements with conventional anisotropic ellipsoids. Orthorhombic AAu3Ga2 (IV, V) are ordered ternary Rb and Cs derivatives of the SrZn5 type structure, demonstrating structural variability within the AAu3Ga2 family. All attempts to prepare an isotypic “NaAu3Ga2” were not successful, but yielded only a similar composition Na13Au41.2Ga30.3 (NaAu3.17Ga2.33) (VI) in a very different structure with two types of cation sites. Crystal orbital Hamilton population (COHP) analysis obtained from tight-binding electronic structure calculations for idealized I–IV via linear muffin-tin-orbital (LMTO) methods emphasized the major contributions of heteroatomic Au–Ga bonding to the structural stability of these compounds. The relative minima (pseudogaps) in the DOS curves for IV

  1. Macrocluster desorption effect caused by single MCI: charges of gold clusters (2-20 nm) desorbed due to electronic processes induced by fission fragment bombardment in nanodispersed gold targets

    International Nuclear Information System (INIS)

    In this work the charge state of the negatively charged gold nanocluster ions (2-20 nm) that were desorbed from nanodispersed gold islet targets by 252Cf fission fragments via electronic processes is studied. Mean cluster charge was calculated as a ratio of mean cluster mass to mean mass-to-charge ratio . Cluster masses were measured by means of a collector technique employing transmission electron microscopy and scanning force microscopy, while m/q was measured by means of a tandem TOF-spectrometer. It is shown that the nanocluster ions are mostly multiply charged (2-16e) and the charge increases non-linearly with the cluster size. The results are discussed

  2. A comparative study between all-electron scalar relativistic calculation and all-electron calculation on the adsorption of hydrogen molecule onto small gold clusters

    Indian Academy of Sciences (India)

    Xiang-Jun Kuang; Xin-Qiang Wang; Gao-Bin Liu

    2013-03-01

    A comparative study between all-electron relativistic (AER) calculation and all-electron (AE) calculation on the H2 molecule adsorption onto small gold clusters has been performed. Compared with the corresponding AuH2 cluster obtained by AE method, the AuH2 cluster obtained by AER method has much shorter Au-H bond-length, much longer H-H distance, larger binding energy and adsorption energy, higher vertical ionization potentials (VIP), greater charge transfer, higher vibrational frequency of Au-H mode and lower vibrational frequency of H-H mode. The delocalization of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) for AuH2 cluster obtained by AER method is obvious. All these characteristics suggest that the scalar relativistic effect might strengthen the Au-H bond and weaken the H-H bond. It is believed that the scalar relativistic effect is favourable to the H2 molecule adsorption onto small gold cluster and the reactivity enhancement of H2 molecule. It may be one of the reasons why the dissociative adsorptions take place in some AuH2 clusters. With increasing size of AuH2 clusters, the influence of scalar relativistic effect becomes more significant. Some further studies focused on the influence of scalar relativistic effect on the adsorption behaviour of other small molecules onto gold clusters are necessary in the future.

  3. Probing the structures of gold-aluminum alloy clusters AuxAly-: a joint experimental and theoretical study

    Science.gov (United States)

    Khetrapal, Navneet Singh; Jian, Tian; Pal, Rhitankar; Lopez, Gary V.; Pande, Seema; Wang, Lai-Sheng; Zeng, Xiao Cheng

    2016-05-01

    Besides the size and structure, compositions can also dramatically affect the properties of alloy nanoclusters. Due to the added degrees of freedom, determination of the global minimum structures for multi-component nanoclusters poses even greater challenges, both experimentally and theoretically. Here we report a systematic and joint experimental/theoretical study of a series of gold-aluminum alloy clusters, AuxAly- (x + y = 7,8), with various compositions (x = 1-3 y = 4-7). Well-resolved photoelectron spectra have been obtained for these clusters at different photon energies. Basin-hopping global searches, coupled with density functional theory calculations, are used to identify low-lying structures of the bimetallic clusters. By comparing computed electronic densities of states of the low-lying isomers with the experimental photoelectron spectra, the global minima are determined. It is found that for y >= 6 there is a strong tendency to form the magic-number square bi-pyramid motif of Al6- in the AuxAly- clusters, suggesting that the Al-Al interaction dominates the Au-Au interaction in the mixed clusters. A closely related trend is that for x > 1, the gold atoms tend to be separated by Al atoms unless only the magic-number Al6- square bi-pyramid motif is present, suggesting that in the small-sized mixed clusters, Al and Au components do not completely mix with one another. Overall, the Al component appears to play a more dominant role due to the high robustness of the magic-number Al6- square bi-pyramid motif, whereas the Au component tends to be either ``adsorbed'' onto the Al6- square bi-pyramid motif if y >= 6, or stays away from one another if x = 6 there is a strong tendency to form the magic-number square bi-pyramid motif of Al6- in the AuxAly- clusters, suggesting that the Al-Al interaction dominates the Au-Au interaction in the mixed clusters. A closely related trend is that for x > 1, the gold atoms tend to be separated by Al atoms unless only the magic

  4. Optical spectroscopy on size selected gold clusters deposited in rare gas matrices

    International Nuclear Information System (INIS)

    We report on the successful 'soft-landing' of size selected Au trimers in solid Krypton matrices. The Au cations are produced by sputtering, mass-selected in a quadrupole mass spectrometer, co-deposited with Krypton on a cooled CaF2 substrate, and neutralized by low energy electrons. The deposition of low kinetic energy cations (10 eV) gives rise to strong excitation bands, detected by the emitted fluorescence light, which are unambiguously attributed to Au trimers. The deposition and fragmentation process is qualitatively discussed. (orig.)

  5. Gold clusters on WO{sub 3} nanoneedles grown via AACVD: XPS and TEM studies

    Energy Technology Data Exchange (ETDEWEB)

    Navio, Cristina [Laboratory of Interaction Chemistry on Plasma Surfaces, University of Mons (Belgium); Vallejos, Stella [MINOS, EMaS, Departament d' Enginyeria Electronica, Universitat Rovira i Virgili, Tarragona (Spain); Department of Chemistry, University College London, London, WC1H 0AJ (United Kingdom); Stoycheva, Toni; Llobet, Eduard; Correig, Xavier [MINOS, EMaS, Departament d' Enginyeria Electronica, Universitat Rovira i Virgili, Tarragona (Spain); Snyders, Rony [Laboratory of Interaction Chemistry on Plasma Surfaces, University of Mons (Belgium); Blackman, Christopher [Department of Chemistry, University College London, London, WC1H 0AJ (United Kingdom); Umek, Polona [Solid State Physcis Department Jozef Stefan Institute, Jamov cesta 39, 1000 Ljubljana (Slovenia); Ke Xiaoxing; Van Tendeloo, Gustaaf [Electron Microscopy for Material Science, University of Antwerp, Antwerp (Belgium); Bittencourt, Carla, E-mail: carla.bittencourt@umons.ac.be [Electron Microscopy for Material Science, University of Antwerp, Antwerp (Belgium)

    2012-06-15

    We have prepared tungsten oxide films decorated with gold particles on Si substrates by aerosol assisted chemical vapor deposition (AACVD) and characterized them using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). SEM shows that the films are composed of needle-like structures and TEM shows that both the needles and the gold particles are crystalline. XPS indicates the presence of oxygen vacancies, i.e. the films are WO{sub 3-x}, and hence the deposited material is composed of semiconducting nanostructures and that the interaction between the gold particles and the WO{sub 3} needles surface is weak. The synthesis of semiconducting tungsten oxide nanostructures decorated with metal particles represents an important step towards the development of sensing devices with optimal properties. - Highlights: Black-Right-Pointing-Pointer Characterization of WO{sub 3} needle-like structures decorated with gold nanoparticles. Black-Right-Pointing-Pointer WO{sub 3} needle-like structures are crystalline. Black-Right-Pointing-Pointer WO{sub 3} needle-like structures are semiconducting.

  6. Neutral and cationic free-space oxygen–silicon clusters SiO{sub n} (1

    Energy Technology Data Exchange (ETDEWEB)

    Forte, G. [Dipartimento di Scienze del Farmaco, Facoltà di Farmacia, Università di Catania, Viale A. Doria, 6, I-95126 Catania (Italy); Angilella, G.G.N., E-mail: giuseppe.angilella@ct.infn.it [Dipartimento di Fisica e Astronomia, Università di Catania, 64, Via S. Sofia, I-95123 Catania (Italy); Scuola Superiore di Catania, Università di Catania, Via S. Nullo, 5/i, I-95123 Catania (Italy); CNISM, UdR Catania, 64, Via S. Sofia, I-95123 Catania (Italy); INFN, Sezione di Catania, 64, Via S. Sofia, I-95123 Catania (Italy); Pittalà, V. [Dipartimento di Scienze del Farmaco, Facoltà di Farmacia, Università di Catania, Viale A. Doria, 6, I-95126 Catania (Italy); March, N.H. [Department of Physics, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Oxford University, Oxford (United Kingdom); Pucci, R. [Dipartimento di Fisica e Astronomia, Università di Catania, 64, Via S. Sofia, I-95123 Catania (Italy); CNISM, UdR Catania, 64, Via S. Sofia, I-95123 Catania (Italy)

    2012-01-09

    Motivated by the theoretical study of Saito and Ono (2011) on three crystalline forms of SiO{sub 2} under pressure, quantum-chemical calculations on various free-space clusters of SiO{sub n} and GeO{sub n} for 1cationic clusters have been examined, for both geometry and equilibrium bond lengths. Coupled clusters and correlation-corrected MP2 calculations are presented. For the cations, we emphasize especially the structural distortions occurring in removing degeneracies. -- Highlights: ► Geometry and structure of various SiO{sub n} and GeO{sub n} clusters. ► Both neutral and cationic clusters. ► Varying coordination numbers. ► Relevant for high pressure studies.

  7. Atomic-scale observation of dynamical fluctuation and three-dimensional structure of gold clusters

    Energy Technology Data Exchange (ETDEWEB)

    Li, Junjie [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, North Zhongshan Road 3663, Shanghai 200062 (China); Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Yin, Deqiang [School of Manufacturing Science and Engineering, Sichuan University, Chengdu 610064 (China); Chen, Chunlin; Lin, Liyang; Wang, Zhongchang, E-mail: zcwang@wpi-aimr.tohoku.ac.jp [Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Li, Qiang [School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093 (China); Sun, Rong [Institute of Engineering Innovation, The University of Tokyo, 2-11-16, Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan); Huang, Sumei, E-mail: smhuang@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, North Zhongshan Road 3663, Shanghai 200062 (China)

    2015-02-28

    Unravelling three-dimensional structures and dynamical fluctuation of metal nanoclusters is critical to understanding reaction process and the origin of catalytic activity in many heterogeneous catalytic systems. We obtain three-dimensional structures of ultra-small Au clusters by combining aberration-corrected scanning transmission electron microscopy, density functional theory calculations, and imaging simulations. The configurations of unique Au clusters are revealed at the atomic scale and the corresponding electronic states are given. The sequential observations reveal a transition of ultra-small Au clusters with about 25 atoms from a near-square to an elongated structure. We also find a transition from two dimensions to three dimensions for the Au clusters. The obtained three-dimensional geometry and associated electronic states help to clarify atomistic mechanism of shape- and number-dependent catalytic activities of Au clusters.

  8. Soft Landing of Mass-Selected Gold Clusters: Influence of Ion and Ligand on Charge Retention and Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Laskin, Julia

    2015-02-01

    Herein, we employ a combination of reduction synthesis in solution, soft landing of mass-selected precursor and product ions, and in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the influence of ion and the length of diphosphine ligands on the charge retention and reactivity of ligated gold clusters deposited onto self-assembled monolayer surfaces (SAMs). Product ions (Au10L42+, (10,4)2+, L = 1,3-bis(diphenyl-phosphino)propane, DPPP) were prepared through in-source collision induced dissociation (CID) and precursor ions [(8,4)2+, L = 1,6-bis(diphenylphosphino)hexane, DPPH] were synthesized in solution for comparison to (11,5)3+ precursor ions ligated with DPPP investigated previously (ACS Nano 2012, 6, 573 and J. Phys. Chem. C. 2012, 116, 24977). Similar to (11,5)3+ precursor ions, the (10,4)2+ product ions are shown to retain charge on 1H,1H,2H,2H-perfluorodecanethiol monolayers (FSAMs). Additional abundant peaks at higher m/z indicative of reactivity are observed in the TOF-SIMS spectrum of (10,4)2+ product ions that are not seen for (11,5)3+ precursor ions. The abundance of (10,4)2+ on 16-mercaptohexadecanoic acid (COOH-SAMs) is demonstrated to be lower than on FSAMs, consistent with partial reduction of charge. The (10,4)2+ product ion on 1-dodecanethiol (HSAMs) exhibits peaks similar to those seen on the COOH-SAM. On the HSAM, higher m/z peaks indicative of reactivity are observed similar to those on the FSAM. The (8,4)2+ DPPH precursor ions are shown to retain charge on FSAMs similar to (11,5)3+ precursor ions prepared with DPPP. An additional peak corresponding to attachment of one gold atom to (8,4)2+ is observed at higher m/z for DPPH-ligated clusters. On the COOH-SAM, (8,4)2+ is less abundant than on the FSAM consistent with partial neutralization. The results indicate that although retention of charge by product ions generated by CID is similar to precursor ions their reactivity during analysis with SIMS is different

  9. Formation of gold clusters on La-Ni mixed oxides and its catalytic performance for isomerization of allylic alcohols to saturated aldehydes

    International Nuclear Information System (INIS)

    Au/NiO catalyzed the isomerization of allylic alcohols to afford saturated aldehydes. La-Ni mixed oxide could stabilize Au(III) and afford gold clusters smaller than 1 nm by H2 reduction. The resulting Au clusters on La-Ni-O exhibited superior catalytic performance to Au/NiO for the isomerization of internal allylic alcohol, 2-octen-1-ol to octanal. (author)

  10. Symmetry breaking in ligand-protected gold clusters probed by nonlinear optics

    Science.gov (United States)

    van Steerteghem, Nick; van Cleuvenbergen, Stijn; Deckers, Steven; Kumara, Chanaka; Dass, Amala; Häkkinen, Hannu; Clays, Koen; Verbiest, Thierry; Knoppe, Stefan

    2016-06-01

    The first hyperpolarizabilities of [Au25(SR)18]-1/0 and Au38(SR)24 clusters were determined by Hyper-Rayleigh Scattering. A strong dependence on the molecular symmetry was observed, and we explore two strategies to destroy the center of inversion in [Au25(SR)18]-1/0, protection by chiral ligands and alloying of the cluster with silver. This may open new avenues to applications of Au : SR clusters in second-order nonlinear optics.The first hyperpolarizabilities of [Au25(SR)18]-1/0 and Au38(SR)24 clusters were determined by Hyper-Rayleigh Scattering. A strong dependence on the molecular symmetry was observed, and we explore two strategies to destroy the center of inversion in [Au25(SR)18]-1/0, protection by chiral ligands and alloying of the cluster with silver. This may open new avenues to applications of Au : SR clusters in second-order nonlinear optics. Electronic supplementary information (ESI) available: Synthesis and characterization of the clusters, details on HRS measurements and DFT calculations. See DOI: 10.1039/c6nr02251k

  11. Symmetry breaking in ligand-protected gold clusters probed by nonlinear optics.

    Science.gov (United States)

    Van Steerteghem, Nick; Van Cleuvenbergen, Stijn; Deckers, Steven; Kumara, Chanaka; Dass, Amala; Häkkinen, Hannu; Clays, Koen; Verbiest, Thierry; Knoppe, Stefan

    2016-06-16

    The first hyperpolarizabilities of [Au25(SR)18](-1/0) and Au38(SR)24 clusters were determined by Hyper-Rayleigh Scattering. A strong dependence on the molecular symmetry was observed, and we explore two strategies to destroy the center of inversion in [Au25(SR)18](-1/0), protection by chiral ligands and alloying of the cluster with silver. This may open new avenues to applications of Au : SR clusters in second-order nonlinear optics. PMID:27264025

  12. Enhancing photothermal cancer therapy by clustering gold nanoparticles into spherical polymeric nanoconstructs

    Science.gov (United States)

    Iodice, Carmen; Cervadoro, Antonio; Palange, AnnaLisa; Key, Jaehong; Aryal, Santosh; Ramirez, Maricela R.; Mattu, Clara; Ciardelli, Gianluca; O'Neill, Brian E.; Decuzzi, Paolo

    2016-01-01

    Gold nanoparticles (AuNPs) have been proposed as agents for enhancing photothermal therapy in cancer and cardiovascular diseases. Different geometrical configurations have been used, ranging from spheres to rods and more complex star shapes, to modulate optical and ablating properties. In this work, multiple, ultra-small 6 nm AuNPs are encapsulated into larger spherical polymeric nanoconstructs (SPNs), made out of a poly(lactic acid-co-glycol acid) (PLGA) core stabilized by a superficial lipid-PEG monolayer. The optical and photothermal properties of the resulting nanoconstructs (Au-SPNs) are modulated by varying the initial loading input of AuNPs, ranging between 25 and 150 μgAu. Au-SPNs exhibit a hydrodynamic diameter varying from ~100 to 180 nm, growing with the gold content, and manifest up to 2-fold increase in thermal energy production per unit mass of gold for an initial input of 100 μgAu. Au-SPNs are stable under physiological conditions up to 7 days and have direct cytotoxic effect on tumor cells. The superior photothermal performance of Au-SPNs is assessed in vitro on monolayers of breast cancer cells (SUM-159) and tumor spheroids of glioblastoma multiforme cells (U87-MG). The encapsulation of small AuNPs into larger spherical nanoconstructs enhances photothermal ablation and could favor tumor accumulation.

  13. Implications of hydrogen/halogen-bond in the stabilization of confined water and anion-water clusters by a cationic receptor

    Science.gov (United States)

    Hoque, Md. Najbul; Das, Gopal

    2016-03-01

    Anion complexation of benzene capped flexible tripodal receptor and solid state stabilization of discrete hybrid anion-water or infinite water clusters by various supramolecular interactions are reported here. The crystal structure of the receptor in protonated states shows all the three arms projected in one direction. We structurally demonstrate discrete fluoride-water cluster [F2-H2O]2- and square shaped chloride-water cluster [Cl2-(H2O)2]2- inside the cationic channel of the receptor. Structural analysis also reveals that these clusters are stabilized inside the channel through active participation of N/C/Ow‧H⋯Ow, N/C/Ow‧H⋯X- (X- = F-, Cl- and I-) H-bonds and electrostatic interactions. Moreover, C-H⋯π and π⋯π types weak intermolecular interactions appear to play crucial role in supramolecular assembly of receptor. Additionally, on treatment with hydroiodic acid (HI) L resulted zwitterionic iodide complex. Crystal structure reveals the presence of S···I halogen bonded dimer, I2···I halogen bond, 1D infinite water chain and neutral iodine molecules. It is comprehensible that ligand basal structure (benzene capped and N-bridge head in two tripodal) play crucial roles in the formation of diverse halide-water cluster. All structures were well examined by different techniques such as NMR, IR, TGA, DSC, PXRD and XRD.

  14. Adsorption of a single gold or silver atom on vanadium oxide clusters.

    Science.gov (United States)

    Ding, Xun-Lei; Wang, Dan; Li, Rui-Jie; Liao, Heng-Lu; Zhang, Yan; Zhang, Hua-Yong

    2016-03-30

    The bonding properties between a single atom and its support have a close relationship with the stability and reactivity of single-atom catalysts. As a model system, the structural and electronic properties of bimetallic oxide clusters MV3Oy(q) (M = Au or Ag, q = 0, ±1, and y = 6-8) are systematically studied using density functional theory. The single noble metal atom Au or Ag tends to be adsorbed on the periphery of the V oxide clusters. Au prefers V sites for oxygen-poor clusters and O sites for oxygen-rich clusters, while Ag prefers O sites for most cases. According to natural population analysis, Au may possess positive or negative charges in the bimetallic oxide clusters, while Ag usually possesses positive charges. The bonding between Au and V has relatively high covalent character according to the bond order analysis. This work may provide some clues for understanding the bonding properties of single noble metal atoms on the support in practical single-atom catalysts, and serve as a starting point for further theoretical studies on the reaction mechanisms of related catalytic systems. PMID:26984782

  15. Investigation of the NH-π hydrogen bond interaction in the aniline-alkene (C2H4,C3H6,C4H8) cluster cations by infrared depletion spectroscopy

    International Nuclear Information System (INIS)

    The vibrational spectra of the NH stretching vibrations of aniline-alkene cluster cations have been measured using infrared depletion method. Aniline-ethene cation showed three strong absorption bands at 3448, 3314 and 3220 cm-1. The comparison with MO calculation has shown that the main intermolecular interaction is the NH-π type hydrogen bond between one of the NH bonds of aniline cation and π-electron of ethene, which is different from that observed for the neutral aniline-ethene cluster. The bands at 3448 and 3220 cm-1 have been assigned to the stretching vibrations of free NH and bonded NH, respectively, and the band at 3314 cm-1 to the binary overtone of the NH2 deformation vibration. Similar results have been obtained for aniline-propene and aniline-butene cluster cations. The red shift of the stretching vibration of free NH bond of aniline cation agreed with that expected from the correlation with the proton affinity of the acceptor molecule obtained for the aniline-aromatic cluster cations (NH-π type)

  16. Hidden Components in Aqueous "Gold-144" Fractionated by PAGE: High-Resolution Orbitrap ESI-MS Identifies the Gold-102 and Higher All-Aromatic Au-pMBA Cluster Compounds.

    Science.gov (United States)

    Alvarez, Marcos M; Chen, Jenny; Plascencia-Villa, Germán; Black, David M; Griffith, Wendell P; Garzón, Ignacio L; José-Yacamán, Miguel; Demeler, Borries; Whetten, Robert L

    2016-07-01

    Experimental and theoretical evidence reveals the resilience and stability of the larger aqueous gold clusters protected with p-mercaptobenzoic acid ligands (pMBA) of composition Aun(pMBA)p or (n, p). The Au144(pMBA)60, (144, 60), or gold-144 aqueous gold cluster is considered special because of its high symmetry, abundance, and icosahedral structure as well as its many potential uses in material and biological sciences. Yet, to this date, direct confirmation of its precise composition and total structure remains elusive. Results presented here from characterization via high-resolution electrospray ionization mass spectrometry on an Orbitrap instrument confirm Au102(pMBA)44 at isotopic resolution. Further, what usually appears as a single band for (144, 60) in electrophoresis (PAGE) is shown to also contain the (130, 50), recently determined to have a truncated-decahedral structure, and a (137, 56) component in addition to the dominant (144, 60) compound of chiral-icosahedral structure. This finding is significant in that it reveals the existence of structures never before observed in all-aromatic water-soluble species while pointing out the path toward elucidation of the thermodynamic control of protected gold nanocrystal formation. PMID:27275518

  17. One-dimensional gold clusters in HP-Ce7Au13+xGe10-x

    International Nuclear Information System (INIS)

    Single crystals of the high-pressure phase Ce7Au13+xGe10-x were obtained by treating CeAuGe at 9.5 GPa and 1473-1523 K in a multi-anvil press. The structure of Ce7Au13.35Ge9.65 was refined on the basis of single-crystal X-ray diffractometer data: new type, Pbam, a = 1571.9(3), b = 1780.3(4), c = 443.58(9) pm, wR2 = 0.0470, 2017 F2 values, 96 variables. Two of the five germanium sites show a small degree of Ge/Au mixing. The gold and germanium atoms build up a complex three-dimensional, covalently bonded [Au13.35Ge9.65] network with Au-Ge distances ranging from 249 to 293 pm. The [Au13.35Ge9.65] network also exhibits a one-dimensional gold cluster with Au-Au distances of 275-301 pm and a weakly bonded germanium dumb-bell with a Ge4-Ge5 bond length of 271 pm. The four crystallographically independent cerium atoms fill cavities of coordination numbers 19 and 20 within the [Au13.35Ge9.65] network. These coordinations are known from other structure types. Consequently one can describe the [Au13.35Ge9.65] structure as an intergrowth variant of EuAuGe, HP-CeAuGe (TiNiSi), CeAu2Ge2 (CePt2Ge2), and Ce3Ag4Ge4 (Gd3Cu4Sn4) related slabs. (orig.)

  18. Gold chloride clusters with Au(III) and Au(I) probed by FT-ICR mass spectrometry and MP2 theory.

    Science.gov (United States)

    Lemke, Kono H

    2014-05-01

    Microsolvated clusters of gold chloride are probed by electrospray ionization mass spectrometry (ESI-MS) and scalar relativistic electronic structure calculations. Electrospray ionization of aqueous AuCl3 leads to mononuclear clusters of types [AuCl2](+)(H2O)n (n = 0-4), [AuOHCl](+)(H2O)n (n = 0-1) and [AuCl2](+)(HCl)2(H2O)n (n = 0-4). In addition, strong ion signals due to dinuclear [Au2Cl5-xOHx](+)(H2O)n (x = 0-1) are present in ESI mass spectra of aqueous AuCl3, with the abundance of individual dinuclear species controlled by the concentration-dependent variation of the precursor complexes [AuCl2-xOHx](+)(H2O)n and AuCl3. Equilibrium structures, energies and thermodynamic properties of mono- and dinuclear gold clusters have been predicted using MP2 and CCSD(T) theory, and these data have been applied to examine the influence of microsolvation on cluster stability. Specifically, results from CCSD(T) calculations indicate that non-covalently bound ion-neutral complexes Au(+)(Cl2)(H2O)n, with formal Au(I), are the dominant forms of mononuclear gold with n = 0-2, while higher hydrates (n > 2) are covalently bound [AuCl2](+)(H2O)n complexes in which gold exists as Au(III). MP2 calculations show that the lowest energy structure of dinuclear gold is an ion-molecule cluster [Au2Cl(Cl2)2](+) consisting of a single-bridged digold-chloronium ion bound end-on to two dichlorine ligands, with two higher energy isomers, single-bridged [Au2Cl3(Cl2)](+) and double-bridged [Au2Cl5](+) clusters. Finally, AuAu interactions in the singly-bridged clusters [Au2Cl(Cl2)2](+)(H2O)n and [Au2Cl3(Cl2)](+)(H2O)n are examined employing a wide range of computational tools, including natural bond order (NBO) analysis and localized orbital locator (LOL) profiles. PMID:24643288

  19. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    International Nuclear Information System (INIS)

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory

  20. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    Energy Technology Data Exchange (ETDEWEB)

    Bréchignac, Philippe, E-mail: philippe.brechignac@u-psud.fr; Falvo, Cyril; Parneix, Pascal; Pino, Thomas; Pirali, Olivier [Institut des Sciences Moléculaires d’Orsay, CNRS UMR8214, Univ Paris-Sud, F-91405 Orsay (France); Garcia, Gustavo A.; Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, B.P. 48, F-91192 Gif-sur-Yvette (France); Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony [IRAP, Université de Toulouse 3 - CNRS, 9 Av. Colonel Roche, B.P. 44346, F-31028 Toulouse Cedex 4 (France); Mulas, Giacomo [INAF - Osservatorio Astronomico di Cagliari, via della scienza 5, I-09047 Selargius (Italy)

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

  1. Photoionization of cold gas phase coronene and its clusters: autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation.

    Science.gov (United States)

    Bréchignac, Philippe; Garcia, Gustavo A; Falvo, Cyril; Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Mulas, Giacomo; Nahon, Laurent

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory. PMID:25362317

  2. The structure of lithium garnets: cation disorder and clustering in a new family of fast Li+ conductors.

    Science.gov (United States)

    Cussen, Edmund J

    2006-01-28

    The structure of the fast lithium-ion conducting garnets Li5La3M2O12 (M = Ta, Nb) reveals Li+ on both tetrahedral and octahedral sites and suggests that the latter are responsible for the observed Li+ mobility via a clustering mechanism. PMID:16493817

  3. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+·UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO2+·UO22+, NpO2+·Th4+, PuO2+·UO22+, and PuO2+·Th4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M-1

  4. Gold-superheavy-element interaction in diatomics and cluster adducts: A combined four-component Dirac-Kohn-Sham/charge-displacement study.

    Science.gov (United States)

    Rampino, Sergio; Storchi, Loriano; Belpassi, Leonardo

    2015-07-14

    The chemistry of superheavy elements (Z ≥ 104) is actively investigated in atom-at-a-time experiments of volatility through adsorption on gold surfaces. In this context, common guidelines for interpretation based on group trends in the periodic table should be used cautiously, because relativistic effects play a central role and may cause predictions to fall short. In this paper, we present an all-electron four-component Dirac-Kohn-Sham comparative study of the interaction of gold with Cn (Z = 112), Fl (Z = 114), and Uuo (Z = 118) versus their lighter homologues of the 6th period, Hg, Pb, and Rn plus the noble gas Xe. Calculations were carried out for Au-E (E = Hg, Cn, Pb, Fl, Xe, Rn, Uuo), Au7- and Au20-E (E = Hg, Cn, Pb, Fl, Rn) complexes, where Au7 (planar) and Au20 (pyramidal) are experimentally determined clusters having structures of increasing complexity. Results are analysed both in terms of the energetics of the complexes and of the electron charge rearrangement accompanying their formation. In line with the available experimental data, Cn and more markedly Fl are found to be less reactive than their lighter homologues. On the contrary, Uuo is found to be more reactive than Rn and Xe. Cn forms the weakest bond with the gold atom, compared to Fl and Uuo. The reactivity of Fl decreases with increasing gold-fragment size more rapidly than that of Cn and, as a consequence, the order of the reactivity of these two elements is inverted upon reaching the Au20-cluster adduct. Density difference maps between adducts and fragments reveal similarities in the behaviour of Cn and Xe, and in that of Uuo and the more reactive species Hg and Pb. These findings are given a quantitative ground via charge-displacement analysis. PMID:26178105

  5. Gold-superheavy-element interaction in diatomics and cluster adducts: A combined four-component Dirac-Kohn-Sham/charge-displacement study

    Science.gov (United States)

    Rampino, Sergio; Storchi, Loriano; Belpassi, Leonardo

    2015-07-01

    The chemistry of superheavy elements (Z ≥ 104) is actively investigated in atom-at-a-time experiments of volatility through adsorption on gold surfaces. In this context, common guidelines for interpretation based on group trends in the periodic table should be used cautiously, because relativistic effects play a central role and may cause predictions to fall short. In this paper, we present an all-electron four-component Dirac-Kohn-Sham comparative study of the interaction of gold with Cn (Z = 112), Fl (Z = 114), and Uuo (Z = 118) versus their lighter homologues of the 6th period, Hg, Pb, and Rn plus the noble gas Xe. Calculations were carried out for Au-E (E = Hg, Cn, Pb, Fl, Xe, Rn, Uuo), Au7- and Au20-E (E = Hg, Cn, Pb, Fl, Rn) complexes, where Au7 (planar) and Au20 (pyramidal) are experimentally determined clusters having structures of increasing complexity. Results are analysed both in terms of the energetics of the complexes and of the electron charge rearrangement accompanying their formation. In line with the available experimental data, Cn and more markedly Fl are found to be less reactive than their lighter homologues. On the contrary, Uuo is found to be more reactive than Rn and Xe. Cn forms the weakest bond with the gold atom, compared to Fl and Uuo. The reactivity of Fl decreases with increasing gold-fragment size more rapidly than that of Cn and, as a consequence, the order of the reactivity of these two elements is inverted upon reaching the Au20-cluster adduct. Density difference maps between adducts and fragments reveal similarities in the behaviour of Cn and Xe, and in that of Uuo and the more reactive species Hg and Pb. These findings are given a quantitative ground via charge-displacement analysis.

  6. Discrete magnesium hydride aggregates: a cationic Mg13H18 cluster stabilized by NNNN-type macrocycles.

    Science.gov (United States)

    Martin, Daniel; Beckerle, Klaus; Schnitzler, Silvia; Spaniol, Thomas P; Maron, Laurent; Okuda, Jun

    2015-03-23

    Large magnesium hydride aggregates [Mg13 (Me3 TACD)6 (μ2 -H12 )(μ3 -H6 )][A]2 ((Me3 TACD)H=1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; A=AlEt4 , AlnBu4 , B{3,5-(CF3 )2 C6 H3 }4 ) were synthesized stepwise from alkyl complexes [Mg2 (Me3 TACD)R3 ] (R=Et, nBu) and phenylsilane in the presence of additional Mg(II) ions. The central magnesium atom is octahedrally coordinated by six hydrides as in solid α-MgH2 of the rutile type. Further coordination to six magnesium atoms leads to a substructure of seven edge-sharing octahedra as found in the hexagonal layer of brucite (Mg(OH)2 ). Upon protonolysis in the presence of 1,2-dimethoxyethane (DME), this cluster was degraded into a tetranuclear dication [Mg2 (Me3 TACD)(μ-H)2 (DME)]2 [A]2 . PMID:25651417

  7. Electronic Structure and Bonding of Icosahedral Core-Shell Gold-Silver Nanoalloy Clusters Au_(144-x)Ag_x(SR)_60

    OpenAIRE

    Malola, Sami; Häkkinen, Hannu

    2011-01-01

    Atomically precise thiolate-stabilized gold nanoclusters are currently of interest for many cross-disciplinary applications in chemistry, physics and molecular biology. Very recently, synthesis and electronic properties of "nanoalloy" clusters Au_(144-x)Ag_x(SR)_60 were reported. Here, density functional theory is used for electronic structure and bonding in Au_(144-x)Ag_x(SR)_60 based on a structural model of the icosahedral Au_144(SR)_60 that features a 114-atom metal core with 60 symmetry-...

  8. Spectroscopic Properties of Novel Aromatic Metal Clusters: NaM4 (M=Al, Ga, In) and their Cations and Anions

    Energy Technology Data Exchange (ETDEWEB)

    Balasubramanian, K; Zhao, C

    2004-03-17

    The ground and several excited states of metal aromatic clusters, namely NaM4 and NaM{sub 4}{sup {+-}} (M=Al, Ga, In) clusters have been investigated by employing complete activespace self-consistent-field (CASSCF) followed by Multi-reference singles and doubles configuration interaction (MRSDCI) computations that included up to 10 million configurations and other methods. The ground states NaM{sub 4}{sup -} of aromatic anions are found to be symmetric C{sub 4v} ({sup 1}A{sub 1}) electronic states with ideal square pyramid geometries. While the ground state of NaIn4 is also predicted to be a symmetric C{sub 4v} ({sup 2}A{sub 1}) square pyramid, the ground state of the NaAl4 cluster is found to have a C{sub 2v} ({sup 2}A{sub 1}) pyramid with a rhombus base and the ground state of NaGa{sub 4} possesses a C{sub 2v} ({sup 2}A{sub 1}) pyramid with a rectangle base. In general these structures exhibit 2 competing geometries, viz., an ideal C{sub 4v} structure and a distorted rhomboidal or rectangular pyramid structure (C{sub 2v}). All of the ground states of the NaM{sub 4}{sup +} (M= Al, Ga, In) cations are computed to be C{sub 2v} ({sup 3}A{sub 2}) pyramids with rhombus bases. The equilibrium geometries, vibrational frequencies, dissociation energies, adiabatic ionization potentials, adiabatic electron affinities for the electronic states of NaM{sub 4} (M=Al, Ga, In) and their ions are computed and compared with experimental results and other theoretical calculations. On the basis of our computed excited states energy separations, we have tentatively suggested assignments to the observed X and A states in the anion photoelectron spectra of Al{sub 4}Na{sup -} reported by Li et al. The X state can be assigned to a C{sub 2v} ({sup 2}A{sub 1}) rhomboidal pyramid. The A state observed in the anion spectrum is assigned to the first excited state ({sup 2}B{sub 1}) of the neutral NaAl{sub 4} with the C{sub 4v} symmetry. The assignments of the excited states are consistent with

  9. Small gold species supported on alumina. A computational study of {alpha}-Al{sub 2}O{sub 3}(0001) and {gamma}-Al{sub 2}O{sub 3}(001) using an embedded-cluster approach

    Energy Technology Data Exchange (ETDEWEB)

    Nasluzov, Vladimir A. [Institute of Chemistry and Chemical Technology, Russian Academy of Sciences, Krasnoyarsk (Russian Federation); Siberian Federal University, Krasnoyarsk (Russian Federation); Shulimovich, Tatyana V.; Shor, Aleksey M. [Institute of Chemistry and Chemical Technology, Russian Academy of Sciences, Krasnoyarsk (Russian Federation); Bukhtiyarov, Valery I. [Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk (Russian Federation); Roesch, Notker [Department Chemie and Catalysis Research Center, Technische Universitaet Muenchen, Garching (Germany)

    2010-05-15

    We calculated the structures of and analyzed the bonding in adsorption complexes of small gold species Au{sub n} on {alpha}-Al{sub 2}O{sub 3}(0001), n=1-6, and {gamma}-Al{sub 2}O{sub 3}(001), n=1-5. We applied a scalar-relativistic gradient-corrected density functional (DF) method to cluster models of the support that were embedded in an extended elastic polarizable environment (EPE). The shortest Au-O distances, 204-211 pm, are consistent with extended X-ray adsorption fine structure (EXAFS) data for gold clusters on alumina surfaces. The calculated total adsorption energies increase with cluster nuclearity, up to n=4, but drop for larger adsorbed species. In the gas phase, these small gold clusters exhibit a planar structure which they keep, oriented parallel to the surface, as adsorbates on {alpha}-Al{sub 2}O{sub 3}(0001). Unfavorable energy contributions result for larger clusters as their planar shape is notably distorted by the interaction with the support which amounts to 0.5-1.5 eV. On {gamma}-Al{sub 2}O{sub 3}(001), also the larger gold clusters retain their intrinsic planar structure as they adsorb oriented perpendicular to the surface. The corresponding adsorption energies are slightly smaller, 0.3-1.2 eV. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  10. Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging.

    Science.gov (United States)

    Croissant, Jonas G; Zhang, Dingyuan; Alsaiari, Shahad; Lu, Jie; Deng, Lin; Tamanoi, Fuyuhiko; AlMalik, Abdulaziz M; Zink, Jeffrey I; Khashab, Niveen M

    2016-05-10

    Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3(+)). The second drug, doxorubicin (DOX, 32wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3(+), affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments. PMID:27016140

  11. Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging

    KAUST Repository

    Croissant, Jonas G.

    2016-03-23

    Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40 wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3+). The second drug, doxorubicin (DOX, 32 wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3+, affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments.

  12. Electronic, magnetic and structural properties of neutral, cationic and anionic Fe{sub 2}S{sub 2}, Fe{sub 3}S{sub 4} and Fe{sub 4}S{sub 4} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Tazibt, S; Bouarab, S; Ziane, A [Laboratoire de Physique et Chimie Quantique, Universite Mouloud Mammeri de Tizi-Ouzou, BP No 17 RP, 15000 Tizi-Ouzou (Algeria); Parlebas, J C [Institut de Physique et Chimie des Materiaux de Strasbourg, UMR 7504 CNRS-UDS, 23 rue du Loess, BP 43, 67034 Strasbourg cedex 2 (France); Demangeat, C, E-mail: sbouarab_said@mail.ummto.d [Institut de Physique, 3 rue de l' Universite 67000 Strasbourg (France)

    2010-08-28

    This work reports density functional calculations of geometric, electronic and magnetic properties of freestanding iron-sulfur Fe{sub 2}S{sub 2}, Fe{sub 3}S{sub 4} and Fe{sub 4}S{sub 4} clusters which are the ones most frequently contained in proteins. We investigate neutral, anionic and cationic clusters using a method that employs linear combinations of atomic orbitals as basis sets, nonlocal norm-conserving pseudopotentials and a generalized gradient approximation to exchange and correlation. The results are discussed in connection with available experimental data. We mainly show that the ground-state geometries of these free clusters are consistent with their structures in core proteins and they are the same in the neutral, anionic and cationic states, but with small distortions. In all cases, an antiferromagnetic order between Fe atoms is always preferred to ferromagnetic and paramagnetic ones. The geometric distortions induced by magnetism decrease with cluster size and the maximum deviation between Fe-Fe distances is 11% in Fe{sub 2}S{sub 2}, but only 4% in Fe{sub 3}S{sub 4} and 3% in Fe{sub 4}S{sub 4} clusters.

  13. Clustering

    Directory of Open Access Journals (Sweden)

    Jinfei Liu

    2013-04-01

    Full Text Available DBSCAN is a well-known density-based clustering algorithm which offers advantages for finding clusters of arbitrary shapes compared to partitioning and hierarchical clustering methods. However, there are few papers studying the DBSCAN algorithm under the privacy preserving distributed data mining model, in which the data is distributed between two or more parties, and the parties cooperate to obtain the clustering results without revealing the data at the individual parties. In this paper, we address the problem of two-party privacy preserving DBSCAN clustering. We first propose two protocols for privacy preserving DBSCAN clustering over horizontally and vertically partitioned data respectively and then extend them to arbitrarily partitioned data. We also provide performance analysis and privacy proof of our solution..

  14. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH3)n and (NH3BH3)n ionized at 10.51 eV

    Science.gov (United States)

    Yuan, Bing; Shin, Joong-Won; Bernstein, Elliot R.

    2016-04-01

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH3BH3) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH3BH3)n and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms and potential energy surfaces for ionized NH3BH3, NH3, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH3)xH+ dominate ammonia cluster mass spectra: our calculations show that formation of (NH3)n-1H+ and NH2 from the nascent (NH3)n+ has the lowest energy barrier for the system. The only common features for the (NH3)n+ and (NH3BH3)n+ mass spectra under these conditions are found to be NHy+ (y = 0,…,4) at m/z = 14-18. Molecular ions with both 11B and 10B isotopes are observed, and therefore, product ions observed for the (NH3BH3)n cluster system derive from (NH3BH3)n clusters themselves, not from the NH3 moiety of NH3BH3 alone. NH3BH2+ is the most abundant ionization product in the (NH3BH3)n+ cluster spectra: calculations support that for NH3BH3+, an H atom is lost from the BH3 moiety with an energy barrier of 0.67 eV. For (NH3BH3)2+ and (NH3BH3)3+ clusters, a Bδ+⋯Hδ-⋯δ-H⋯δ+B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH3BH3)n+ (n = 2, 3) dissociation is the breaking of the Bδ+⋯Hδ-⋯δ-H⋯δ+B moiety, leading to the subsequent release of H2 from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF natural bond orbital

  15. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH3)n and (NH3BH3)n ionized at 10.51 eV.

    Science.gov (United States)

    Yuan, Bing; Shin, Joong-Won; Bernstein, Elliot R

    2016-04-14

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH3BH3) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH3BH3)n and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms and potential energy surfaces for ionized NH3BH3, NH3, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH3)xH(+) dominate ammonia cluster mass spectra: our calculations show that formation of (NH3)n-1H(+) and NH2 from the nascent (NH3)n(+) has the lowest energy barrier for the system. The only common features for the (NH3)n(+) and (NH3BH3)n(+) mass spectra under these conditions are found to be NHy(+) (y = 0,…,4) at m/z = 14-18. Molecular ions with both (11)B and (10)B isotopes are observed, and therefore, product ions observed for the (NH3BH3)n cluster system derive from (NH3BH3)n clusters themselves, not from the NH3 moiety of NH3BH3 alone. NH3BH2(+) is the most abundant ionization product in the (NH3BH3)n(+) cluster spectra: calculations support that for NH3BH3(+), an H atom is lost from the BH3 moiety with an energy barrier of 0.67 eV. For (NH3BH3)2(+) and (NH3BH3)3(+) clusters, a B(δ+)⋯H(δ-)⋯(δ-)H⋯(δ+)B bond can form in the respective cluster ions, generating a lower energy, more stable ion structure. The first step in the (NH3BH3)n(+) (n = 2, 3) dissociation is the breaking of the B(δ+)⋯H(δ-)⋯(δ-)H⋯(δ+)B moiety, leading to the subsequent release of H2 from the latter cluster ion. The overall reaction mechanisms calculated are best represented and understood employing a CASSCF

  16. Combined Experimental and Theoretical DFT Study of Molecular Nanowires Negative Differential Resistance and Interaction With Gold Clusters

    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Kratochvílová, Irena; Zambova, A.; Mbindyo, J.; Mallouk, T. E.; Mayer, T. S.

    2005-01-01

    Roč. 18, č. 2 (2005), s. 201-206. ISSN 1292-8941 R&D Projects: GA AV ČR 1ET400400413; GA AV ČR IAA400400501 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100520 Keywords : molecule/gold transport interfaces * single molecules * metal nanowires * junctions Subject RIV: CG - Electrochemistry Impact factor: 2.503, year: 2005

  17. Plane-wave Density Functional Theory Study of the Electronic and Structural Properties of Ionized and Neutral Small Gold Clusters

    OpenAIRE

    Min, Byeong June; Shin, Won Chul; Park, Jae Ik

    2016-01-01

    We studied the structural and the electronic properties of ionized and neutral small Au clusters via plane wave pseudopotential calculations. All except the anionic heptamer favor one-dimensional zigzag structures or two-dimensional arrangements of triangles. The HOMO-LUMO (highest occupied molecular orbital - lowest unoccupied molecular orbital) gap, the ionization energy, and the electronic affinity exhibit even-odd variation as a function of the cluster size.

  18. Systematic Study of Au6 to Au12 Gold Clusters on MgO(100) F Centers Using Density-Functional Theory

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Hammer, Bjørk

    2012-01-01

    We present an optimized genetic algorithm used in conjunction with density-functional theory in the search for stable gold clusters and O2 adsorption ensembles in F centers at MgO(100). For Au8 the method recovers known structures and identifies several more stable ones. When O2 adsorption is...

  19. Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

    International Nuclear Information System (INIS)

    This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N′-dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 ± 5 nm upon excitation at 345 ± 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV–vis absorption spectra, UV–vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.

  20. Bridging gold in electron-deficient Al2Au(n)(0/-) and BAlAu(n)(0/-) (n = 1-3) clusters.

    Science.gov (United States)

    Yao, Wen-Zhi; Liu, Bing-Tao; Lu, Zhang-Hui; Li, Si-Dian

    2013-06-20

    The geometrical and electronic structures of the electron-deficient dialuminum aurides Al2Aun(0/-) and hybrid boron-aluminum aurides BAlAun(0/-) (n = 1-3) are systematically investigated based on the density and wave function theories. Ab initio theoretical evidence strongly suggests that bridging gold atoms exist in the ground states of C2v Al2Au(-) ((3)B1), C2v Al2Au ((2)B1), C2v Al2Au2(-) ((2)A1), C2v Al2Au2 ((1)A1), Cs Al2Au3(-) ((1)A'), and D3h Al2Au3 ((2)A1), which prove to possess an Al-Au-Al τ bond. For BAlAun(0/-) (n = 1-3) mixed clusters, bridging B-Au-Al units only exist in Cs BAlAu3(-) ((1)A') and Cs BAlAu3 ((2)A'), whereas Cs BAlAu(-) ((3)A''), Cs BAlAu ((2)A''), Cs BAlAu2(-) ((2)A'), and Cs BAlAu2 ((1)A') do not possess a bridging gold, as demonstrated by the fact that B-Al and B-Au exhibit significantly stronger electronic interaction than Al-Au in the same clusters. Orbital analyses indicate that Au 6s contributes approximately 98%-99% to the Au-based orbital in these Al-Au-Al/B-Au-Al interactions, whereas Au 5d contributes 1%-2%. The adiabatic and vertical detachment energies of Al2Aun(-) (n = 1-3) are calculated to facilitate future experimental characterizations. The results obtained in this work establish an interesting τ bonding model (Al-Au-Al/B-Au-Al) for electron-deficient systems in which Au 6s plays a major factor. PMID:23718624

  1. Change in magnetic and structural properties of FeRh thin films by gold cluster ion beam irradiation with the energy of 1.67 MeV/atom

    International Nuclear Information System (INIS)

    The effect of energetic cluster ion beam irradiation on magnetic and structural properties of FeRh thin films have been investigated. The cluster ions used in the present studies consist of a few gold atoms with the energy of 1.67 MeV/gold atom. Saturation magnetization of the sample irradiated with Au3 cluster ion beam (280 emu/cc) is larger than that for the irradiated sample with Au1 ion beam (240 emu/cc) for the same irradiation ion fluence. These results can also be confirmed by the X-ray magnetic circular dichroism (XMCD) measurement; the XMCD signal for Au3 cluster ion irradiation is larger than that for Au1 ion irradiation. Since the ion beam irradiation induced magnetization of FeRh is significantly correlated with the amount of the lattice defects in the samples, cluster ion beam irradiation can be considered to effectively introduce the lattice defects in B2-type FeRh rather than the single ion beam. Consequently, cluster ion irradiation is better than single ion irradiation for the viewpoint of saturation magnetization, even if the same irradiation energy is deposited in the samples

  2. Change in magnetic and structural properties of FeRh thin films by gold cluster ion beam irradiation with the energy of 1.67 MeV/atom

    Science.gov (United States)

    Koide, T.; Saitoh, Y.; Sakamaki, M.; Amemiya, K.; Iwase, A.; Matsui, T.

    2014-05-01

    The effect of energetic cluster ion beam irradiation on magnetic and structural properties of FeRh thin films have been investigated. The cluster ions used in the present studies consist of a few gold atoms with the energy of 1.67 MeV/gold atom. Saturation magnetization of the sample irradiated with Au3 cluster ion beam (280 emu/cc) is larger than that for the irradiated sample with Au1 ion beam (240 emu/cc) for the same irradiation ion fluence. These results can also be confirmed by the X-ray magnetic circular dichroism (XMCD) measurement; the XMCD signal for Au3 cluster ion irradiation is larger than that for Au1 ion irradiation. Since the ion beam irradiation induced magnetization of FeRh is significantly correlated with the amount of the lattice defects in the samples, cluster ion beam irradiation can be considered to effectively introduce the lattice defects in B2-type FeRh rather than the single ion beam. Consequently, cluster ion irradiation is better than single ion irradiation for the viewpoint of saturation magnetization, even if the same irradiation energy is deposited in the samples.

  3. Change in magnetic and structural properties of FeRh thin films by gold cluster ion beam irradiation with the energy of 1.67 MeV/atom

    Energy Technology Data Exchange (ETDEWEB)

    Koide, T.; Iwase, A. [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Saitoh, Y. [Japan Atomic Energy Agency, Takasaki, Gunma 370-1292 (Japan); Sakamaki, M.; Amemiya, K. [High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Matsui, T., E-mail: t-matsui@21c.osakafu-u.ac.jp [Research Organization for the 21st Century, Osaka Prefecture University Sakai, Osaka 599-8531 (Japan)

    2014-05-07

    The effect of energetic cluster ion beam irradiation on magnetic and structural properties of FeRh thin films have been investigated. The cluster ions used in the present studies consist of a few gold atoms with the energy of 1.67 MeV/gold atom. Saturation magnetization of the sample irradiated with Au3 cluster ion beam (280 emu/cc) is larger than that for the irradiated sample with Au1 ion beam (240 emu/cc) for the same irradiation ion fluence. These results can also be confirmed by the X-ray magnetic circular dichroism (XMCD) measurement; the XMCD signal for Au3 cluster ion irradiation is larger than that for Au1 ion irradiation. Since the ion beam irradiation induced magnetization of FeRh is significantly correlated with the amount of the lattice defects in the samples, cluster ion beam irradiation can be considered to effectively introduce the lattice defects in B2-type FeRh rather than the single ion beam. Consequently, cluster ion irradiation is better than single ion irradiation for the viewpoint of saturation magnetization, even if the same irradiation energy is deposited in the samples.

  4. Fluorescent or not? Size-dependent fluorescence switching for polymer-stabilized gold clusters in the 1.1-1.7 nm size range.

    Science.gov (United States)

    Schaeffer, Nicolas; Tan, Bien; Dickinson, Calum; Rosseinsky, Matthew J; Laromaine, Anna; McComb, David W; Stevens, Molly M; Wang, Yiqian; Petit, Laure; Barentin, Catherine; Spiller, David G; Cooper, Andrew I; Lévy, Raphaël

    2008-09-14

    The synthesis of fluorescent water-soluble gold nanoparticles by the reduction of a gold salt in the presence of a designed polymer ligand is described, the size and fluorescence of the particles being controlled by the polymer to gold ratio; the most fluorescent nanomaterial has a 3% quantum yield, a 1.1 nm gold core and a 6.9 nm hydrodynamic radius. PMID:18758601

  5. Electronic Structure and Bonding of Icosahedral Core-Shell Gold-Silver Nanoalloy Clusters Au_(144-x)Ag_x(SR)_60

    CERN Document Server

    Malola, Sami

    2011-01-01

    Atomically precise thiolate-stabilized gold nanoclusters are currently of interest for many cross-disciplinary applications in chemistry, physics and molecular biology. Very recently, synthesis and electronic properties of "nanoalloy" clusters Au_(144-x)Ag_x(SR)_60 were reported. Here, density functional theory is used for electronic structure and bonding in Au_(144-x)Ag_x(SR)_60 based on a structural model of the icosahedral Au_144(SR)_60 that features a 114-atom metal core with 60 symmetry-equivalent surface sites, and a protecting layer of 30 RSAuSR units. In the optimal configuration the 60 surface sites of the core are occupied by silver in Au_84Ag_60(SR)_60. Silver enhances the electron shell structure around the Fermi level in the metal core, which predicts a structured absorption spectrum around the onset (about 0.8 eV) of electronic metal-to-metal transitions. The calculations also imply element-dependent absorption edges for Au(5d) \\rightarrow Au(6sp) and Ag(4d) \\rightarrow Ag(5sp) interband transit...

  6. 密度泛函理论研究CO与Aun Mg-1、Au-1n(n=1~8)团簇的相互作用%Density Functional Study of Interaction of CO with Anion Mg-Doped Gold Clusters and Anion Gold Clusters

    Institute of Scientific and Technical Information of China (English)

    王必利; 王慧; 张明; 何曼丽

    2014-01-01

    采用密度泛函理论对CO在阴离子团簇AunMg-1、Au-1n (n=1~8)表面的吸附做了系统研究。结果表明, Aun MgCO-1、Aun CO-1团簇的最稳定结构是在团簇Aun Mg-1、Au-1n 最低能量结构的基础上吸附CO形成,CO的吸附没有改变团簇Aun Mg-1、Au-1n 的最低能量结构;吸附后的CO键长变长,表明CO分子被活化;n取值相同时, Aun MgCO-1的吸附能较低,表明Aun CO-1团簇掺杂Mg后稳定性降低;HOMO-LOMO能隙结果表明Aun MgCO-1、Aun CO-1团簇能隙都具有奇偶振荡的现象。%The adsorption of CO on anion Mg-doped Gold clusters and anion Gold clusters surfaces has been systematically investigated by density functional theory. The result indicates that the most stable structures of AunMgCO-1,AunCO-1(n=1-8) are generated with CO being adsorbed on the lowest energy structures of Aun Mg-1 , Au-1n , and the most stable structures of Aun Mg-1 , Au-1n clusters are not changed by adsorbing CO molecule. The increased CO bond length demonstrates the activation of the CO molecule. The adsorption energy of Aun MgCO-1 is lower indicates the stability of Aun CO-1 is enhanced by Mg-doped. The HOMO-LUMO energy gaps of Aun Mg-1 and Au-1n clusters exhibit an odd-even oscillatory behavior.

  7. O2 adsorption on AunRh n = 1-5 neutral and charged clusters

    Science.gov (United States)

    Buendía, Fernando; Beltrán, Marcela R.

    2016-04-01

    Theoretical evidence is presented for the molecular and dissociative adsorption of O2 on free AunRh neutral, anionic and cationic clusters with 1 to 5 gold atoms, indicating that the stabilization of the activated di-oxygen species is a key factor for the unusual catalytic activities of Au-based catalysts. The structure, stability, for both molecular and dissociative O2 adsorption on AunRh n = 1-5 clusters has been investigated using density-functional theory. To find the transition states, the minimum energy paths have been explored for a few clusters. In general, lower values for the activation energy have been found when compared with the barriers that occur on pure Aun based clusters. The higher binding energies in the AuRh mix favor oxygen dissociation among any other possible reaction paths. The anionic clusters being the most reactive of all. The molecular bonding mechanism to these complexes involves charge transfer to the oxygen molecule with a concomitant activation of the O-O bond to a superoxo-like state. The characteristic planar structures of both pure gold and AuRh clusters prevail for most of the cases here studied. The odd-even characteristic catalytic activation of pure gold clusters is not observed once even a single rhodium atom has been added to the cluster.

  8. Thermal Methane Activation by a Binary V-Nb Transition-Metal Oxide Cluster Cation: A Further Example for the Crucial Role of Oxygen-Centered Radicals

    Czech Academy of Sciences Publication Activity Database

    Wang, Z. C.; Liu, J. W.; Schlangen, M.; Weiske, T.; Schröder, Detlef; Sauer, J.; Schwarz, H.

    2013-01-01

    Roč. 19, č. 35 (2013), s. 11496-11501. ISSN 0947-6539 Institutional support: RVO:61388963 Keywords : binary oxide cluster * density functional calculations * mass spectrometry * methane activation * radical ions Subject RIV: CC - Organic Chemistry Impact factor: 5.696, year: 2013

  9. CO oxidation on gold nanoparticles: Theoretical studies

    DEFF Research Database (Denmark)

    Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

    2005-01-01

    We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...

  10. Investigating the Synthesis of Ligated Metal Clusters in Solution Using a Flow Reactor and Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Olivares, Astrid M.; Laskin, Julia; Johnson, Grant E.

    2014-09-18

    The scalable synthesis of subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth and post-reduction etching are still not well understood. Herein, we demonstrate a temperature-controlled flow reactor for studying cluster formation in solution at well-defined conditions. Employing this technique methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with an adjustable length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates and products synthesized in real time was characterized using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged metal-ligand complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged metal-ligand complexes while hindering the growth of triply charged clusters. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of reduction synthesis in solution.

  11. Nonresonant chemical mechanism in surface-enhanced Raman scattering of pyridine on M@Au12 clusters

    Science.gov (United States)

    Chen, Lei; Gao, Yang; Cheng, Yingkun; Li, Haichao; Wang, Zhigang; Li, Zhengqiang; Zhang, Rui-Qin

    2016-02-01

    By employing density functional theory (DFT), this study presents a detailed analysis of nonresonant surface-enhanced Raman scattering (SERS) of pyridine on M@Au12 (M = V-, Nb-, Ta-, Cr, Mo, W, Mn+, Tc+, and Re+)-the stable 13-atom neutral and charged gold buckyball clusters. Changing the core atom in M@Au12 enabled us to modulate the direct chemical interactions between pyridine and the metal cluster. The results of our calculations indicate that the ground-state chemical enhancement does not increase as the binding interaction strengthens or the transfer charge increases between pyridine and the cluster. Instead, the magnitude of the chemical enhancement is governed, to a large extent, by the charged properties of the metal clusters. Pyridine on M@Au12 anion clusters exhibits strong chemical enhancement of a factor of about 102, but the equivalent increase for pyridine adsorbed on M@Au12 neutral and cation clusters is no more than 10. Polarizability and deformation density analyses clearly show that compared with the neutral and cation clusters, the anion clusters have more delocalized electrons and occupy higher energy levels in the pyridine-metal complex. Accordingly, they produce larger polarizability, leading to a stronger nonresonant enhancement effect.By employing density functional theory (DFT), this study presents a detailed analysis of nonresonant surface-enhanced Raman scattering (SERS) of pyridine on M@Au12 (M = V-, Nb-, Ta-, Cr, Mo, W, Mn+, Tc+, and Re+)-the stable 13-atom neutral and charged gold buckyball clusters. Changing the core atom in M@Au12 enabled us to modulate the direct chemical interactions between pyridine and the metal cluster. The results of our calculations indicate that the ground-state chemical enhancement does not increase as the binding interaction strengthens or the transfer charge increases between pyridine and the cluster. Instead, the magnitude of the chemical enhancement is governed, to a large extent, by the charged

  12. Gold prices

    OpenAIRE

    Joseph G. Haubrich

    1998-01-01

    The price of gold commands attention because it serves as an indicator of general price stability or inflation. But gold is also a commodity, used in jewelry and by industry, so demand and supply affect its pricing and need to be considered when gold is a factor in monetary policy decisions.

  13. Photodissociation of Cerium Oxide Nanocluster Cations.

    Science.gov (United States)

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A

    2016-04-21

    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)). PMID:27035210

  14. Assemblies of gold icosahedra

    OpenAIRE

    Bilalbegovic, G.

    2004-01-01

    Low-dimensional free-standing aggregates of bare gold clusters are studied by the molecular dynamics simulation. Icosahedra of 55 and 147 atoms are equilibrated at T=300 K. Then, their one- and two-dimensional assemblies are investigated. It is found that icosahedra do not coalescence into large drops, but stable amorphous nanostructures are formed: nanowires for one-dimensional and nanofilms for two-dimensional assemblies. The high-temperature stability of these nanostructures is also invest...

  15. Density functional study of structural and electronic properties of maximum-spin n+1Aun-1Ag clusters

    Science.gov (United States)

    Jiang, Zhen-Yi; Hou, Yu-Qin; Lee, Kuo-Hsing; Chu, San-Yan

    The structures and relative stabilities of high-spin n+1Aun-1Ag and nAun-1Ag+ (n = 2-8) clusters have been studied with density functional calculation. We predicted the existence of a number of previously unknown isomers. Our results revealed that all structures of high-spin neutral or cationic Aun-1Ag clusters can be understood as a substitution of an Au atom by an Ag atom in the high-spin neutral or cationic Aun clusters. The properties of mixed gold-silver clusters are strongly sized and structural dependence. The high-spin bimetallic clusters tend to be holding three-dimensional geometry rather than planar form represented in their low-spin situations. Silver atom prefers to occupy those peripheral positions until to n = 8 for high-spin clusters, which is different from its position occupied by light atom in the low-spin situations. Our theoretical calculations indicated that in various high-spin Aun-1Ag neutral and cationic species, 5Au3Ag, 3AuAg and 5Au4Ag+ hold high stability, which can be explained by valence bond theory.

  16. Using Glutamic Acid, Phenylalanine and Tryptophan to Synthesize Capped Gold Nanoparticles

    OpenAIRE

    Kamyar Khoshnevisan; Mohammad Barkhi; Nasim Bararpour; Shahram Tangestaninejad; Azim Akbarzadeh; Davood Zare

    2011-01-01

    Introduction: The study and investigation of gold nanoparticles produced by amino acid is one of the interesting and applied issues in nanotechnology. In this study, amino acids were used to reduce gold cations as well as an agent to cap gold nanoparticles. In fact, strong bound of amino groups to amino acid and protein on the gold nanoparticles surface indicate the medical applications of these materials. Methods: In this study, gold nanoparticles were prepared and functionalized by using so...

  17. Nonlinear optical studies of single gold nanoparticles

    NARCIS (Netherlands)

    Dijk, Meindert Alexander van

    2007-01-01

    Gold nanoparticles are spherical clusters of gold atoms, with diameters typically between 1 and 100 nanometers. The applications of these particles are rather diverse, from optical labels for biological experiments to data carrier for optical data storage. The goal of my project was to develop new

  18. Gold Returns

    OpenAIRE

    Robert J. Barro; Sanjay P. Misra

    2013-01-01

    From 1836 to 2011, the average real rate of price change for gold in the United States is 1.1% per year and the standard deviation is 13.1%, implying a one-standard-deviation confidence band for the mean of (0.1%, 2.1%). The covariances of gold's real rate of price change with consumption and GDP growth rates are small and statistically insignificantly different from zero. These negligible covariances suggest that gold's expected real rate of return--which includes an unobserved dividend yiel...

  19. Gold metal liquid-like droplets.

    Science.gov (United States)

    Smirnov, Evgeny; Scanlon, Micheál D; Momotenko, Dmitry; Vrubel, Heron; Méndez, Manuel A; Brevet, Pierre-Francois; Girault, Hubert H

    2014-09-23

    Simple methods to self-assemble coatings and films encompassing nanoparticles are highly desirable in many practical scenarios, yet scarcely any examples of simple, robust approaches to coat macroscopic droplets with continuous, thick (multilayer), reflective and stable liquid nanoparticle films exist. Here, we introduce a facile and rapid one-step route to form films of reflective liquid-like gold that encase macroscopic droplets, and we denote these as gold metal liquid-like droplets (MeLLDs). The present approach takes advantage of the inherent self-assembly of gold nanoparticles at liquid-liquid interfaces and the increase in rates of nanoparticle aggregate trapping at the interface during emulsification. The ease of displacement of the stabilizing citrate ligands by appropriate redox active molecules that act as a lubricating molecular glue is key. Specifically, the heterogeneous interaction of citrate stabilized aqueous gold nanoparticles with the lipophilic electron donor tetrathiafulvalene under emulsified conditions produces gold MeLLDs. This methodology relies exclusively on electrochemical reactions, i.e., the oxidation of tetrathiafulvalene to its radical cation by the gold nanoparticle, and electrostatic interactions between the radical cation and nanoparticles. The gold MeLLDs are reversibly deformable upon compression and decompression and kinetically stable for extended periods of time in excess of a year. PMID:25184343

  20. Gold Monetization and Gold Discipline

    OpenAIRE

    1980-01-01

    The paper is a study of the price level and relative price effects of a policy to monetize gold and fix its price at a given future time and at the then prevailing nominal price. Price movements are analyzed both during the transition to the gold standard and during the post-monetization period. The paper also explores the adjustments to fiat money which are necessary to ensure that this type of gold monetization is non-inflationary. Finally, some conditions which produce a run on the governm...

  1. Gold monetization and gold discipline

    OpenAIRE

    Flood, Robert P.; Peter M. Garber

    1981-01-01

    The paper is a study of the price level and relative price effects of a policy to monetize gold and fix its price at a given future time and at the then prevailing nominal price. Price movements are analyzed both during the transition to the gold standard and during the post-monetization period. The paper also explores the adjustments to fiat money which are necessary to ensure that this type of gold monetization is non-inflationary. Finally, some conditions which produce a run on the governm...

  2. Ground state of naphthyl cation: Singlet or triplet?

    Energy Technology Data Exchange (ETDEWEB)

    Dutta, Achintya Kumar; Vaval, Nayana, E-mail: np.vaval@ncl.res.in; Pal, Sourav, E-mail: s.pal@ncl.res.in [Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008 (India); Manohar, Prashant U. [Department of Chemistry, BITS Pilani, Pilani Campus (India)

    2014-03-21

    We present a benchmark theoretical investigation on the electronic structure and singlet-triplet(S-T) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calculations reported in previous theoretical studies. However, the triplet states obtained in the two structural isomers of naphthyl cation are completely different. The triplet state in 1-naphthyl cation is (π,σ) type, whereas in 2-naphthyl cation it is (σ,σ{sup ′}) type. The S-T gaps in naphthyl cations and the relative stability ordering of the singlet and the triplet states are highly sensitive to the basis-set quality as well as level of correlation, and demand for inclusion of perturbative triples in the coupled-cluster ansatz.

  3. Host–guest properties of the trinuclear arene–ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+

    OpenAIRE

    Therrien, Bruno; Vieille-Petit, Ludovic; Süss-Fink, Georg

    2009-01-01

    The trinuclear arene–ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+, containing a μ3-oxo cap and three arene ligands that span a hydrophobic pocket above the metal skeleton, has been crystallised as tetrafluoroborate salt in the presence of various guest molecules. The host–guest complexes have been characterised by single-crystal X-ray structure analysis. With chloroform as the guest molecule, a CHCl3 molecule sits perfectly in the hydrophobic pocket, the hydrogen atom being encapsulated...

  4. World Gold Markets, Istanbul Gold Exchange and Gold Risk Management

    OpenAIRE

    Serdar Citak

    1999-01-01

    The establishment of Istanbul Gold Exchange (IGE) is the most important stage in the Turkish gold sector restructuring process. IGE has provided a competitive formation in prices and the price differential between Turkey and international markets has been cut dramatically. Today, Turkish investors can buy and sell gold in international prices in the IGE Precious Metals Market. Gold is accepted as a hedge tool against inflation and as a safe haven in economic crisis, world-wide. Gold is the on...

  5. Green Gold

    International Nuclear Information System (INIS)

    The main purpose of this work is to offer a general panoramic of the processes or experiences pilot that are carried out in the Project Green Gold, as strategy of environmental sustainability and organizational invigoration in Choco, especially in the 12 communities of the municipalities of Tado and Condoto. It is also sought to offer a minimum of information on the techniques of handmade production and to show the possibilities to carry out in a rational way the use and use of the natural resources. The Project Green Gold is carried out by the Corporation Green Gold (COV) and co-financed with resources of international and national character, the intervention of the financial resources it achievement mainly for the use of clean processes in the extraction stages and metals benefit. The project is centered primarily in the absence of use of products or toxic substances as the mercury, fair trade, organizational invigoration, execution of 11 approaches and certification of the metals Gold and Platinum. The COV, it has come executing the proposal from the year 2001 with the premise of contributing to the balance between the rational exploitation of the natural resources and the conservation of the environment in the Choco. In the project they are used technical handmade characteristic of the region framed inside the mining activity and production activities are diversified in the productive family units. Those producing with the support of entities of juridical character, specify the necessary game rules for the extraction and products commercialization

  6. Goldenphilicity: Luminescent gold compounds

    International Nuclear Information System (INIS)

    In the solids and molecules different types of bonds are presented depending on the involved atoms, covalent bonds are common among elements of open shell, where more bond orbitals are filled than anti bond orbitals. It is expected that ionic bonds among closed shell atoms which have charges of opposite sign. Bonds type Van der Waals are presented among molecules which have a bipolar moment. It would not be expected bonds among zero charge species, or more generally with the same nominal charge and in any case the attractive forces would be very small. In fact it is expected that two metallic cations to be repelled each other. There recently is evidence that in organic or organometallic compounds could exist attractive interactions between two cations of the d8 -d10 -s2 families. These bonds are weak but stronger than those of Van der Waals. They are compared with the hydrogen bonds. In this work it was reviewed some examples in which the goldenphilicity plays an important role in the luminescence that the gold complexes present. Examples of mono, bi and trinuclear and the structures that these organometallic compounds could take are examined. (Author)

  7. Relative yields, mass distributions and energy spectra of cluster ions sputtered from niobium under keV atomic and polyatomic gold ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Belykh, S.F. E-mail: serbel@ariel.tashkent.su; Habets, B.; Rasulev, U.Kh.; Samartsev, A.V.; Stroev, L.V.; Veryovkin, I.V

    2000-04-01

    In the present work, the comparative studies of relative yields, mass distributions and kinetic energy spectra of secondary Nb{sub n}{sup +} ions (n=1-16) sputtered from niobium target by atomic and polyatomic Au{sub m}{sup -} projectiles (m=1-3) with the energy E{sub 0}=6-18 keV/atom have been carried out. The strong effect of anomalously high non-additivity of metal sputtering as positive large cluster ions under polyatomic ion bombardment was found. The comparison and discussion of the results obtained for Nb and for Ta are presented.

  8. Enhanced thermal lens effect in gold nanoparticle-doped Lyotropic liquid crystal by nanoparticle clustering probed by Z-scan technique

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, S.L.; Lenart, V.M., E-mail: sgomez@uepg.br [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Dept. de Fisica; Turchiello, R.T. [Universidade Federal Tecnologica do Parana (UFTPR), Ponta Grossa, PR (Brazil). Dept. de Fisica; Goya, G.F. [Department of Condensed Matter Physics, Aragon Institute of Nanoscience, Zaragoza (Spain)

    2015-10-01

    This work presents an experimental study of the thermal lens effect in Au nanoparticles-doped lyotropic liquid crystals under cw 532 nm optical excitation. Spherical Au nanoparticles of about 12 nm were prepared by Turkevich’s method, and the lyotropic liquid crystal was a ternary mixture of SDS, 1-DeOH, and water that exhibits an isotropic phase at room temperature. The lyotropic matrix induces aggregation of the nanoparticles, leading to a broad and a red-shifted surface plasmon resonance. The thermal nonlinear optical refraction coefficient n{sub 2} increases as a power of number density of nanoparticles, being possible to address this behavior to nanoparticle clustering. (author)

  9. Infrared spectroscopy of mass-selected metal carbonyl cations

    Science.gov (United States)

    Ricks, A. M.; Reed, Z. E.; Duncan, M. A.

    2011-04-01

    Metal carbonyl cations of the form M(CO)n+ are produced in a molecular beam by laser vaporization in a pulsed nozzle source. These ions, and their corresponding rare gas atom "tagged" analogs, M(CO)n(RG)m+, are studied with mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region and with density functional theory computations. The number of infrared-active bands, their frequency positions, and their relative intensities provide distinctive patterns allowing determination of the geometries and electronic structures of these complexes. Cobalt penta carbonyl and manganese hexacarbonyl cations are compared to isoelectronic iron pentacarbonyl and chromium hexacarbonyl neutrals. Gold and copper provide examples of "non-classical" carbonyls. Seven-coordinate carbonyls are explored for the vanadium group metal cations (V +, Nb + and Ta +), while uranium cations provide an example of an eight-coordinate carbonyl.

  10. Cation-cation interaction in neptunyl(V) compounds

    International Nuclear Information System (INIS)

    The original manuscript was prepared by Professor N.N. Krot of Institute of Physical Chemistry, Russian Academy of Sciences, in 1997. Saeki tried to translate that into Japanese and to add some new data since 1997. The contents include the whole picture of cation-cation interactions mainly in 5-valence neptunium compounds. Firstly, characteristic structures of neptunium are summarized of the cation-cation bonding in compounds. Secondly, it is mentioned how the cation-cation bonding affects physical and chemical properties of the compounds. Then, characterization-methods for the cation-cation bonding in the compounds are discussed. Finally, the cation-cation interactions in compounds of other actinide-ions are shortly reviewed. (author)

  11. The mechanism of elution of gold cyanide from activated carbon

    Science.gov (United States)

    van Deventer, J. S. J.; van der Merwe, P. F.

    1994-12-01

    Numerous articles have appeared on the mechanism of the adsorption of gold cyanide onto activated carbon. In contrast, little information is available on the mechanism of elution of the adsorbed gold. It is the objective of this article to formulate such a mechanism on the basis of batch and column elution tests without analyzing adsorbed species on the carbon directly. The presence of spectator cations (M n+) enhances the formation of M n+{Au(CN){2/-}} n ion pairs on the carbon, which in turn suppress the elution of gold cyanide. The dynamics of removal of these cations determine the horizontal position of the gold peak in an elution profile. When the concentration of cations in the eluant is high and no cyanide is present in the solution or on the carbon, very little desorption of gold is observed. The quantitative effect of the concentration of spectator cations on the equilibrium for desorption of aurocyanide can be estimated from the elution profiles for gold and cations. Free cyanide in the eluant, which causes some competitive adsorption of cyanide with aurocyanide, therefore plays a minor role at the elevated temperatures used in industry. A more important effect of cyanide is its reaction with functional groups on the carbon, the products of which passivate the surface for adsorption of aurocyanide, and thereby cyanide promotes the elution of aurocyanide. The degree of passivation, which is determined to a large extent by the temperature of pretreatment, also affects the elution of cations and the degradation/adsorption of cyanide itself. Reactivation of the carbon surface occurs when the adsorbed/decomposed cyanide is removed by the eluant. At high temperatures of pretreatment, such as used in practice, it is not necessary to include a reactivation term in the mathematical model for elution.

  12. New Trends in Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2014-07-01

    Full Text Available Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growing fields in science and is proven by the promising applications in several fields, such as green chemistry and environmental catalysis, in the synthesis of single-walled carbon nanotubes, as modifiers of Ni catalysts for methane steam and dry reforming reactions and in biological and electrochemistry applications. The range of reactions catalyzed by gold, as well as the suitability of different supports and the influence of the preparation conditions have been widely explored and optimized in applied research [2]. Gold catalysts appeared to be very different from the other noble metal-based catalysts, due to their marked dependence on the preparation method, which is crucial for the genesis of the catalytic activity. Several methods, including deposition-precipitation, chemical vapor deposition and cation adsorption, have been applied for the preparation of gold catalysts over reducible oxides, like TiO2. Among these methods, deposition-precipitation has been the most frequently employed method for Au loading, and it involves the use of tetrachloroauric (III acid as a precursor. On the other hand, the number of articles dealing with Au-loaded acidic supports is smaller than that on basic supports, possibly because the deposition of [AuCl4]− or [AuOHxCl4−x]− species on acidic supports is difficult, due to their very low point of zero charge. Despite this challenge, several groups have reported the use of acidic zeolites as supports for gold. Zeolites

  13. Going for Gold

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    While the international gold price in February hit the highest point in 25 years at $541.20 per ounce for futures delivery, a new gold rush is sweeping across China. According to the World Gold Council, the London-based gold marketing organization funded by leading global gold mining firms, the purchase of gold products in China grew by 9 percent in the first nine

  14. Templating growth of gold nanostructures with a CdSe quantum dot array

    Science.gov (United States)

    Paul, Neelima; Metwalli, Ezzeldin; Yao, Yuan; Schwartzkopf, Matthias; Yu, Shun; Roth, Stephan V.; Müller-Buschbaum, Peter; Paul, Amitesh

    2015-05-01

    In optoelectronic devices based on quantum dot arrays, thin nanolayers of gold are preferred as stable metal contacts and for connecting recombination centers. The optimal morphology requirements are uniform arrays with precisely controlled positions and sizes over a large area with long range ordering since this strongly affects device performance. To understand the development of gold layer nanomorphology, the detailed mechanism of structure formation are probed with time-resolved grazing incidence small-angle X-ray scattering (GISAXS) during gold sputter deposition. Gold is sputtered on a CdSe quantum dot array with a characteristic quantum dot spacing of ~7 nm. In the initial stages of gold nanostructure growth, a preferential deposition of gold on top of quantum dots occurs. Thus, the quantum dots act as nucleation sites for gold growth. In later stages, the gold nanoparticles surrounding the quantum dots undergo a coarsening to form a complete layer comprised of gold-dot clusters. Next, growth proceeds dominantly via vertical growth of gold on these gold-dot clusters to form an gold capping layer. In this capping layer, a shift of the cluster boundaries due to ripening is found. Thus, a templating of gold on a CdSe quantum dot array is feasible at low gold coverage.

  15. First-Principles Investigation of Ag-Doped Gold Nanoclusters

    OpenAIRE

    Fei-Yue Fan; Yi She; Qing-Fen Liu; Liang-An Zhang; Yuan-Ming Sun; Di Wu; Xiao-Dong Zhang; Pei-Xun Liu; Mei-Li Guo

    2011-01-01

    Gold nanoclusters have the tunable optical absorption property, and are promising for cancer cell imaging, photothermal therapy and radiotherapy. First-principle is a very powerful tool for design of novel materials. In the present work, structural properties, band gap engineering and tunable optical properties of Ag-doped gold clusters have been calculated using density functional theory. The electronic structure of a stable Au20 cluster can be modulated by incorporating Ag, and the HOMO–LUM...

  16. Gold in Modern Economy

    OpenAIRE

    Boryshkevych Olena V.

    2014-01-01

    The article studies the role of gold in modern economy. It analyses dynamics and modern state of the gold market. It studies volumes of contracts in exchange and off-exchange markets. In order to reveal changes of key features of the gold market, it focuses on the study of gold demand volumes, studies volumes and geographical changes in the world gold mining, and analyses volumes of monetary gold of central banks and its share in gold and currency reserves. It analyses price fluctuations in t...

  17. Novel Catalysis by Gold: A Modern Alchemy

    Science.gov (United States)

    Haruta, Masatake

    Gold has long been neglected as a catalyst because of its chemical inertness. However, when gold is deposited as nanoparticles on carbon and polymer materials as well as on base metal oxides and hydroxides, it exhibits unique catalytic properties for many reactions such as CO oxidation at a temperature as low as 200 K, gas phase direct epoxidation of propylene, and aerobic oxidation of glucose to gluconic acid. The structure-catalytic activity correlations are discussed with emphasis on the contact structure, support selection, and the size control of gold particles. Gold clusters with diameters smaller than 2 nm are expected to exhibit novel properties in catalysis, optics, and electronics depending on the size (number of atoms), shape, and the electronic and chemical interaction with the support materials. The above achievements and attempts can be regarded as a modern alchemy that creates valuables by means of the noblest element with little practical use.

  18. Density Functional Study of Electronic and Structural Properties of Gold-Cadmium Selenide/Telluride Nanoclusters

    Directory of Open Access Journals (Sweden)

    Shimeles T. Bulbula

    2015-01-01

    gold electrodes decrease as cluster size increases, whereas the binding energy shows a reverse relationship with the cluster size. However, a few clusters show special properties like AuCd2Se3 and AuCd2Te3 clusters.

  19. Colloidal gold--low density lipoprotein conjugates as membrane receptor probes.

    OpenAIRE

    Handley, D. A.; Arbeeny, C M; Witte, L D; Chien, S

    1981-01-01

    We have developed a method for conjugating low density lipoproteins (LDL) with colloidal gold. Conjugation, complete after 1 min, occurs by electrostatic adsorption of the LDL to the negatively charged gold particle. Each conjugate consists of approximately eight biologically active LDL molecules clustered around a central 19-nm gold granule. Acidic (pH 4), alkaline (pH 9), or high ionic (600 milliosmolar NaCl) environments do not dissociate the conjugate. Colloidal gold is an electron-dense,...

  20. Cationic Antimicrobial Peptide Cytotoxicity

    OpenAIRE

    Laverty, Garry; Gilmore, Brendan

    2014-01-01

    Fluorescence microscopy serves as a valuable tool for assessing the structural integrity and viability of eukaryotic cells. Through the use of calcein AM and the DNA stain 4,6-diamidino-2 phenylindole (DAPI), cell viability and membrane integrity can be qualified. Our group has previously shown the ultra-short cationic antimicrobial peptide H-OOWW-NH2; the amphibian derived 27-mer peptide Maximin-4and the ultra-short lipopeptide C12-OOWW-NH2 to be effective against a range of bacterial biofil...

  1. Surface-confined crown ether-capped gold nanoclusters: investigation on their electrochemical behavior

    International Nuclear Information System (INIS)

    A new ligand 18-crown-6–aminoethanethiol (18C6–AET), in which crown ether–ammonium ion interaction was exploited, had been designed and synthesized. An estimated HOMO–LUMO gap of 0.259 eV for the 18C6–AET complex indicated a definite interaction between 18C6 and AET. Consequently, multivalent interactions interplayed for the stabilization of gold nanoclusters resulting in confined cationic clusters having a diameter in 2–5-nm range in aqueous medium. The modified indium tin oxide electrodes with immobilized 18C6–AET-capped gold nanoclusters represented a metal–insulator–semiconductor junction across which the characteristic interfacial electron transport was unraveled. A heterogeneous electron transfer rate constant of 5.082 s−1 with a transfer coefficient of 0.51 was obtained for the quasi-reversible process, complying with a core-to-core electron hopping transport along with through-bond tunneling across the linker.

  2. Electronic shell structure and chemisorption on gold nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Ask Hjorth; Kleis, Jesper; Thygesen, Kristian Sommer;

    2011-01-01

    We use density functional theory (DFT) to investigate the electronic structure and chemical properties of gold nanoparticles. Different structural families of clusters are compared. For up to 60 atoms we optimize structures using DFT-based simulated annealing. Cluster geometries are found to...

  3. How many gold atoms make gold metal?

    OpenAIRE

    Häkkinen, Hannu; Malola, Sami

    2015-01-01

    It is well known that a piece of gold is an excellent metal: it conducts heat and electricity, it is malleable to work out for jewellery or thin coatings, and it has the characteristic golden colour. How do these everyday properties – familiar from our macroscopic world – change when a nanometre-size chunk of gold contains only 100, 200 or 300 atoms?

  4. Frontiers in Gold Chemistry

    OpenAIRE

    Mohamed, Ahmed A.

    2015-01-01

    Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of g...

  5. Surface reconstruction precursor to melting in Au309 clusters

    Directory of Open Access Journals (Sweden)

    Fuyi Chen

    2011-09-01

    Full Text Available The melting of gold cluster is one of essential properties of nanoparticles and revisited to clarify the role played by the surface facets in the melting transition by molecular dynamics simulations. The occurrence of elaborate surface reconstruction is observed using many-body Gupta potential as energetic model for 309-atom (2.6 nm decahedral, cuboctahedral and icosahedral gold clusters. Our results reveal for the first time a surface reconstruction as precursor to the melting transitions. The surface reconstruction lead to an enhanced melting temperature for (100 faceted decahedral and cuboctahedral cluster than (111 faceted icosahedral gold cluster, which form a liquid patch due to surface vacancy.

  6. Gold-Mining

    DEFF Research Database (Denmark)

    Raaballe, J.; Grundy, B.D.

    2002-01-01

    operating gold mines. Asymmetric information on the reserves in the mine implies that, at a high enough price of gold, the manager of high type finds the extraction value of the company to be higher than the current market value of the non-operating gold mine. Due to this under valuation the maxim of market...... structure, objectives of the manager, and convenience yield)....

  7. Synthesis, optical and electrical properties of Au nanoparticles/cationic polythiophene polyelectrolyte composites

    Czech Academy of Sciences Publication Activity Database

    Kazim, Samrana; Bondarev, M.; Vohlídal, J.; Procházka, M.; Pfleger, Jiří

    Thessaloniki : LTFN, Aristotle University, 2010 - (Logothetidis, S.). s. 94 [International Symposium on Flexible Organic Electronics /3./. 06.07.2010-09.07.2010, Ouranoupolis] EU Projects: European Commission(XE) 247745 - FlexNet Institutional research plan: CEZ:AV0Z40500505 Keywords : gold nanoparticles * cationic polythiophene Subject RIV: CD - Macromolecular Chemistry

  8. Theoretical Investigation on the Adsorption of Ag+ and Hydrated Ag+ Cations on Clean Si(111)Surface

    Institute of Scientific and Technical Information of China (English)

    SHENG Yong-Li; LI Meng-Hua; WANG Zhi-Guo; LIU Yong-Jun

    2008-01-01

    In this paper,the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111)surface were investigated by using cluster(Gaussian 03)and periodic(DMol3)ab initio calculations.Si(111)surface was described with cluster models(Si14H17 and Si22H21)and a four-silicon layer slab with periodic boundary conditions.The effect of basis set superposition error(BSSE)was taken into account by applying the counterpoise correction.The calculated results indicated that the binding energies between hydrated Ag+ cations and clean Si(111)surface are large,suggesting a strong interaction between hydrated Ag+ cations and the semiconductor surface.With the increase of number,water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Ag+ cation.The Ag+ cation in aqueous solution will safely attach to the clean Si(111)surface.

  9. Development and experimental application of a gold liquid metal ion source

    Energy Technology Data Exchange (ETDEWEB)

    Davies, N.; Weibel, D.E.; Blenkinsopp, P.; Lockyer, N.; Hill, R.; Vickerman, J.C

    2003-01-15

    A liquid metal ion source (LMIS) based upon a gold/germanium eutectic has been developed. The LMIS emits a variety of ions including monatomic gold and gold clusters. Gold ions have been utilised for SIMS analysis of the polypeptide gramicidin and the polymer poly(ethylene-terepthalate) (PET). It has been found that monatomic gold (Au{sup +}) increases secondary ion yields up to a factor of four compared to gallium, for both gramicidin and PET. The Au{sub 3}{sup +} cluster produces a strong non-linear increase in yield over monatomic gold, for both gramicidin and PET. This effect is greatest at high mass, the yield for the gramicidin molecular ion increasing by a factor of over 60. No evidence has been found to suggest increased fragmentation as a result of cluster ion bombardment. The LMIS also exhibits good static SIMS imaging capacity.

  10. Catalysis by gold

    CERN Document Server

    Bond, Geoffrey C; Thompson, David T

    2006-01-01

    Gold has traditionally been regarded as inactive as a catalytic metal. However, the advent of nanoparticulate gold on high surface area oxide supports has demonstrated its high catalytic activity in many chemical reactions. Gold is active as a heterogeneous catalyst in both gas and liquid phases, and complexes catalyse reactions homogeneously in solution. Many of the reactions being studied will lead to new application areas for catalysis by gold in pollution control, chemical processing, sensors and fuel cell technology. This book describes the properties of gold, the methods for preparing g

  11. Electronic shell structure and chemisorption on gold nanoparticles

    OpenAIRE

    Larsen, Ask Hjorth; Kleis, Jesper; Thygesen, Kristian Sommer; Nørskov, J. K.; Jacobsen, Karsten Wedel

    2013-01-01

    We use density functional theory (DFT) to investigate the electronic structure and chemical properties of gold nanoparticles. Different structural families of clusters are compared. For up to 60 atoms we optimize structures using DFT-based simulated annealing. Cluster geometries are found to distort considerably, creating large band gaps at the Fermi level. For up to 200 atoms we consider structures generated with a simple EMT potential and clusters based on cuboctahedra and icosahedra. All t...

  12. Ion exchange behaviour of polymeric zirconium cations

    International Nuclear Information System (INIS)

    Polymeric zirconium cations formed in weakly acid solutions (pH2) are taken up strongly into macroporous cation exchange resins, while uptake into normal cation exchange resins (pore diameter about 1 nm) is low. Macroporous cation exchange resins loaded with polymeric Zr cations are shown to function as ligand exchange sorbents. (Authors)

  13. Electroless selective deposition of gold nano-array for silicon nanowires growth

    Directory of Open Access Journals (Sweden)

    Ruiz-Gomes E.

    2014-01-01

    Full Text Available Nanopatterns of gold clusters on a large surface of oriented Si(111 substrates, from the galvanic displacement of gold salt (via the spontaneous reduction of AuCl4 -, are demonstrated in this work. The Si substrate is patterned by Focused Ion Beam (FIB prior to being dipped in a gold solution. Here, we show that these patterns lead to successful control of the position and size of gold clusters. Sequential patterning reveals a powerful maskless alternative to surface preparation prior to Si nanowire growth

  14. Using Glutamic Acid, Phenylalanine and Tryptophan to Synthesize Capped Gold Nanoparticles

    Directory of Open Access Journals (Sweden)

    Kamyar Khoshnevisan

    2011-01-01

    Full Text Available Introduction: The study and investigation of gold nanoparticles produced by amino acid is one of the interesting and applied issues in nanotechnology. In this study, amino acids were used to reduce gold cations as well as an agent to cap gold nanoparticles. In fact, strong bound of amino groups to amino acid and protein on the gold nanoparticles surface indicate the medical applications of these materials. Methods: In this study, gold nanoparticles were prepared and functionalized by using solution reduction containing gold cations with optimum concentration (0.005 M, and also prepared by using glutamic acid, phenylalanine and tryptophan with optimum concentration (0.025 M. Results: The investigation of optimum condition for gold solution and amino acids and also determination of gold nanoparticles were done by UV-Vis. The nanoparticles size were reported 5-20, 10-20 and 20-30 nm respectively by transmission electron microscopy and dynamic light scattering techniques, which is appropriate for biological activities. Conclusion: The comparison of the data from experimental and quantum calculations demonstrated that amino acids have strong band when they are conjugated by anion state. Free carboxylic groups of capped gold nanoparticles with glutamic acid are one of the suitable and capable beads for binding to biological agents.

  15. Controlled Aspect Ratios of Gold Nanorods in Reduction-Limited Conditions

    Directory of Open Access Journals (Sweden)

    Jong-Yeob Kim

    2011-01-01

    Full Text Available Aspect ratios of gold nanorods have been finely modified in reduction-limited conditions via two electrochemical ways: by changing the amount of a growth solution containing small gold clusters in the presence of already prepared gold nanorods as seeds or by changing electrolysis time in the presence or absence of a silver plate. While the atomic molar ratio of gold in the growth solution to gold in the seed solution is critical in the former method, the relative molar ratio of gold ions to silver ions in the electrolytic solution is important in the latter way for the control of the aspect ratios of gold nanorods. The aspect ratios of gold nanorods decrease with an increase of electrolysis time in the absence of a silver plate, but they increase with an increase of electrolysis time in the presence of a silver plate.

  16. Preparation of gold nanocluster bioconjugates for electron microscopy.

    Science.gov (United States)

    Heinecke, Christine L; Ackerson, Christopher J

    2013-01-01

    In this chapter, we describe types of gold nanoparticle-biomolecule conjugates and their use in electron microscopy. Included are two detailed protocols for labeling an IgG antibody with gold monolayer protected clusters. The first approach is a direct bonding approach that utilizes the ligand place exchange reaction. The second approach describes NHS-EDC coupling of Au(144)(pMBA)(60) with IgG. Also included are various characterization techniques for determining labeling efficiency. PMID:23086882

  17. Correlation between the Increasing Conductivity of Aqueous Solutions of Cation Chlorides with Time and the “Salting-Out” Properties of the Cations

    Directory of Open Access Journals (Sweden)

    Nada Verdel

    2016-02-01

    Full Text Available The time-dependent role of cations was investigated by ageing four different aqueous solutions of cation chlorides. A linear correlation was found between the cations’ Setchenov coefficient for the salting-out of benzene and the increase in the conductivity with time. The conductivity of the structure-breaking cations or the chaotropes increased more significantly with time than the conductivity of the kosmotropes. Since larger water clusters accelerate the proton or hydroxyl hopping mechanism, we propose that the structuring of the hydration shells of the chaotropes might be spontaneously enhanced over time.

  18. Gold Thione Complexes

    Directory of Open Access Journals (Sweden)

    Francesco Caddeo

    2014-08-01

    Full Text Available The reaction of the ligand Et4todit (4,5,6,7-Tetrathiocino-[1,2-b:3,4-b']-diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione with gold complexes leads to the dinuclear gold(I complexes [{Au(C6F5}2(Et4todit] and [Au(Et4todit]2(OTf2, which do not contain any gold-gold interactions, or to the gold(III derivative [{Au(C6F53}2(Et4todit]. The crystal structures have been established by X-ray diffraction studies and show that the gold centers coordinate to the sulfur atoms of the imidazoline-2-thione groups.

  19. Gold Thione Complexes

    OpenAIRE

    Francesco Caddeo; Vanesa Fernández-Moreira; Massimiliano Arca; Antonio Laguna; Vito Lippolis; M. Concepción Gimeno

    2014-01-01

    The reaction of the ligand Et4todit (4,5,6,7-Tetrathiocino-[1,2-b:3,4-b']-diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione) with gold complexes leads to the dinuclear gold(I) complexes [{Au(C6F5)}2(Et4todit)] and [Au(Et4todit)]2(OTf)2, which do not contain any gold-gold interactions, or to the gold(III) derivative [{Au(C6F5)3}2(Et4todit)]. The crystal structures have been established by X-ray diffraction studies and show that the gold centers coordinate to the sulfur atoms of the imidazoline-2-t...

  20. Polymer Protected Gold Nanoparticles

    OpenAIRE

    Shan, Jun

    2006-01-01

    Polymer protected gold nanoparticles have successfully been synthesized by both "grafting-from" and "grafting-to" techniques. The synthesis methods of the gold particles were systematically studied. Two chemically different homopolymers were used to protect gold particles: thermo-responsive poly(N-isopropylacrylamide), PNIPAM, and polystyrene, PS. Both polymers were synthesized by using a controlled/living radical polymerization process, reversible addition-fragmentation chain transfer (RAFT)...

  1. Magic Gold Nanotubes

    OpenAIRE

    SENGER, R. Tuğrul; DAĞ, Sefa; ÇIRACI, Salim

    2005-01-01

    In recent ultra-high-vacuum transmission-electron-microscopy experiments evidence is found for the formation of suspended gold single-wall nanotubes (SWNTs) composed of five helical strands. Similar to carbon nanotubes, the (n,m) notation defines the structure of the gold SWNTs. Experimentally, only the (5,3) tube has been observed to form among several other possible alternatives. Using first-principles calculations we demonstrate that gold atoms can form both freestanding and tip-...

  2. Gold as an investment

    OpenAIRE

    Zemánek, Adam

    2015-01-01

    Bachelor thesis was created to understand investments in gold, to analyse the develop-ment of its price, discussing the reasons why people should invest in gold. Moreover, it introduces different forms of availability and possible earnings from investing in gold. First part is focused on describing important properties of this valuable commodity. Second part of the thesis analyses specific possibilities of investments and compares them with each other from the point of view of an investor.

  3. A Gold Bubble?

    OpenAIRE

    Dirk G Baur; Kristoffer Glover

    2012-01-01

    In this paper we use a test developed by Phillips et al. (2011) to identify a bubble in the gold market. We find that the price of gold followed an explosive price process between 2002 and 2012 interrupted only briefly by the subprime crisis in 2008. We also provide a theoretical foundation for such bubble tests based on a behavioural model of heterogeneous agents and demonstrate that periods of explosive price behaviour are consistent with increased chartist activity in the gold market. The ...

  4. Two new polyoxovanadate clusters templated through cysteamine

    Indian Academy of Sciences (India)

    K Pavani; S Upreti; A Ramanan

    2006-03-01

    Two new fully oxidized polyoxovanadate cluster-based solids (C4N2S2H14)2[H2V10O28]$\\cdot$4H2O, 1 and (C4N2S2H14)5[H4V15O42]2.10H2O, 2 are crystallized under self-assembly process in the presence of cysteamine. In both 1 and 2, cysteamines are oxidized forming disulphide linkages and occur as counter cations. The organic cations assemble around V10O28 cluster anions in 1 whereas they aggregate around V15O42 clusters in 2. pH appears to be the structure determinant in the occurrence of decavanadate cluster in 1 and pentadecavanadate in 2, with the same counter cation.

  5. Molecular modeling of organic corrosion inhibitors: why bare metal cations are not appropriate models of oxidized metal surfaces and solvated metal cations.

    Science.gov (United States)

    Kokalj, Anton

    2014-01-01

    The applicability of various models of oxidized metal surfaces - bare metal cations, clusters of various size, and extended (periodic) slabs - that are used in the field of quantum-chemical modeling of corrosion inhibitors is examined and discussed. As representative model systems imidazole inhibitor, MgO surface, and solvated Mg(2+) ion are considered by means of density-functional-theory calculations. Although the results of cluster models are prone to cluster size and shape effects, the clusters of moderate size seem useful at least for qualitative purposes. In contrast, the bare metal cations are useless not only as models of oxidized surfaces but also as models of solvated cations, because they bind molecules several times stronger than the more appropriate models. In particular, bare Mg(2+) binds imidazole by 5.9 eV, while the slab model of MgO(001) by only 0.35 eV. Such binding is even stronger for 3+ cations, e.g., bare Al(3+) binds imidazole by 17.9 eV. The reasons for these fantastically strong binding energies are discussed and it is shown that the strong bonding is predominantly due to electron charge transfer from molecule to metal cation, which stems from differences between molecular and metal ionization potentials. PMID:25125117

  6. Colloidal gold: Pt. 1

    International Nuclear Information System (INIS)

    Two basic approaches are used in the preparation of colloidal gold solutions. One is the disintegration of metallic gold rods by an electric arc operating in a liquid medium. The other more general approach is the synthesis of particles from gold salts using either appropriate reducing agents or radiation. X-rays with the results from electron microscopy were used for size determination. The growth, nucleation and coagulation of the particles were studied. The morphology and structure charateristics of colloidal gold particles were investigated by means of electron microscopy and are also described

  7. Cluster Automorphisms

    OpenAIRE

    Assem, Ibrahim; Schiffler, Ralf; Shramchenko, Vasilisa

    2010-01-01

    In this article, we introduce the notion of cluster automorphism of a given cluster algebra as a $\\ZZ$-automorphism of the cluster algebra that sends a cluster to another and commutes with mutations. We study the group of cluster automorphisms in detail for acyclic cluster algebras and cluster algebras from surfaces, and we compute this group explicitly for the Dynkin types and the Euclidean types.

  8. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl-, NO3-, C2O42-) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu2+, Zn2+, UO22+, Fe3+, Nd3+, Eu3+, Th4+) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author)

  9. Subcellular localization of alkaline phosphatase in Bacillus licheniformis 749/C by immunoelectron microscopy with colloidal gold

    International Nuclear Information System (INIS)

    Subcellular distribution of the alkaline phosphatase of Bacillus licheniformis 749/C was determined by an immunoelectron microscopy method. Anti-alkaline phosphatase antibody labeled with 15- to 18-nm colloidal gold particles (gold-immunoglobulin G [IgG] complex) were used for the study. Both the plasma membrane and cytoplasmic material were labeled with the gold-IgG particles. These particles formed clusters in association with the plasma membrane; in contrast, in the cytoplasm the particles were largely dispersed, and only a few clusters were found. The gold-IgG binding was quantitatively estimated by stereological analysis of labeled, frozen thin sections. This estimation of a variety of control samples showed that the labeling was specific for the alkaline phosphatase. Cluster formation of the gold -IgG particles in association with the plasma membrane suggests that existence of specific alkaline phosphatase binding sites (receptors) in the plasma membrane of B. licheniformis 749/C. 27 references, 6 figures, 1 table

  10. Gold in the investment portfolio

    OpenAIRE

    Demidova-Menzel, Nadeshda; Heidorn, Thomas

    2007-01-01

    The paper examines the key drivers of gold investment. Since 2000 the gold price has risen drastically, making gold an interesting add-on to a portfolio. As gold futures have negative roll returns, gold pool accounts are characterized by high credit risk and physical possession of gold means high transaction costs, Xetra-Gold might be the most efficient way to enter the market. Xetra-Gold is a product created by the Deutsche Börse in 2007, which is handled like a security but can be exchanged...

  11. BROOKHAVEN: High energy gold

    International Nuclear Information System (INIS)

    On April 24, Brookhaven's Alternating Gradient Synchrotron (AGS) started to deliver gold ions at 11.4 GeV per nucleon (2,000 GeV per ion) to experimenters who were delighted not only to receive the world's highest energy gold beam but also to receive it on schedule

  12. Gold in the Books

    Institute of Scientific and Technical Information of China (English)

    江河

    2002-01-01

    In the present Chinese market, more and more businessmen turn to the profit-making trade. Even some counters in the bookstores are selling gold rings, necklaces, bracelets, etc. One day a school teacher asked a store assistant,“Why are you selling gold in your bookstore?”

  13. Gold in psoriatic arthopathy.

    OpenAIRE

    Richter, M B; Kinsella, P; Corbett, M

    1980-01-01

    It has been suggested that gold is not effective in psoriatic arthropathy. We did not agree and therefore did a retrospective study of 98 patients. Gold had been given to 27 and was effective in 22, 14 of whom are still receiving it. The incidence of side effects was low and comparable to those in rheumatoid arthritis.

  14. Star-like superalkali cations featuring planar pentacoordinate carbon.

    Science.gov (United States)

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-28

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5 (+) range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically

  15. Star-like superalkali cations featuring planar pentacoordinate carbon

    Science.gov (United States)

    Guo, Jin-Chang; Tian, Wen-Juan; Wang, Ying-Jin; Zhao, Xue-Feng; Wu, Yan-Bo; Zhai, Hua-Jin; Li, Si-Dian

    2016-06-01

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5+ (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5+ (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5+ range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and

  16. First-Principles Investigation of Ag-Doped Gold Nanoclusters

    Directory of Open Access Journals (Sweden)

    Fei-Yue Fan

    2011-05-01

    Full Text Available Gold nanoclusters have the tunable optical absorption property, and are promising for cancer cell imaging, photothermal therapy and radiotherapy. First-principle is a very powerful tool for design of novel materials. In the present work, structural properties, band gap engineering and tunable optical properties of Ag-doped gold clusters have been calculated using density functional theory. The electronic structure of a stable Au20 cluster can be modulated by incorporating Ag, and the HOMO–LUMO gap of Au20−nAgn clusters is modulated due to the incorporation of Ag electronic states in the HOMO and LUMO. Furthermore, the results of the imaginary part of the dielectric function indicate that the optical transition of gold clusters is concentration-dependent and the optical transition between HOMO and LUMO shifts to the low energy range as the Ag atom increases. These calculated results are helpful for the design of gold cluster-based biomaterials, and will be of interest in the fields of radiation medicine, biophysics and nanoscience.

  17. A novel method of supporting gold nanoparticles on MWCNTs: Synchrotron X-ray reduction

    Institute of Scientific and Technical Information of China (English)

    Kuan-Nan Lin; Tsung-Yeh Yang; Hong-Ming Lin; Yeu-Kuang Hwu; She-Huang Wu; Chung-Kwei Lin

    2007-01-01

    Gold nanoparticles decorating the surface of multiwalled carbon nanotubes (MWCNTs) are prepared by photochemical reduction. The gold clusters form different interesting geometrical faceted shapes in accordance to time duration of synchrotron X-ray irradiation. The shape of nanogold could be spherical, rod-like, or triangular. Carbon nanotubes serve as optimal templates for the heterogeneous nucleation of gold nanocrystals. These nanocrystal structures are characterized by transmission electron microscope (TEM) and element analysis by energy dispersive spectroscopy (EDS).

  18. Subcellular localization of alkaline phosphatase in Bacillus licheniformis 749/C by immunoelectron microscopy with colloidal gold.

    OpenAIRE

    Tinglu, G; Ghosh, A.; Ghosh, B K

    1984-01-01

    Subcellular distribution of the alkaline phosphatase of Bacillus licheniformis 749/C was determined by an immunoelectron microscopy method. Anti-alkaline phosphatase antibody labeled with 15- to 18-nm colloidal gold particles (gold-immunoglobulin G [IgG] complex) were used for the study. Both the plasma membrane and cytoplasmic material were labeled with the gold-IgG particles. These particles formed clusters in association with the plasma membrane; in contrast, in the cytoplasm the particles...

  19. Optimization of PAMAM-gold nanoparticle conjugation for gene therapy

    OpenAIRE

    Figueroa, Elizabeth R.; Lin, Adam Y.; Yan, Jiaxi; Luo, Laureen; Foster, Aaron E.; Drezek, Rebekah A.

    2013-01-01

    The development of efficient and biocompatible non-viral vectors for gene therapy remains a great challenge, and exploiting the properties of both nanoparticle carriers and cationic polymers is an attractive approach. In this work, we have developed gold nanoparticle (AuNP) polyamidoamine (PAMAM) conjugates for use as non-viral transfection agents. AuPAMAM conjugates were prepared by crosslinking PAMAM dendrimers to carboxylic-terminated AuNPs via EDC and sulfo-NHS chemistry. EDC and sulfo-NH...

  20. Adsorption of polyelectrolytes on silica and gold surfaces

    OpenAIRE

    Altamirano, M. A. Balderas; Camacho, R.; E. Pérez; Goicochea, A. Gama

    2016-01-01

    The results of a study that helps understand the mechanisms of adsorption of polyelectrolytes on particles, using numerical simulation methods, specifically the one known as dissipative particle dynamics are reported here. The adsorption of cationic polyelectrolytes of two different polymerization degrees interacting with two types of surfaces, one made of gold and the other of silica is predicted and compared. We find that a more negatively charged wall does not necessarily adsorb more catio...

  1. Hollow Gold Cages and Their Topological Relationship to Dual Fullerenes.

    Science.gov (United States)

    Trombach, Lukas; Rampino, Sergio; Wang, Lai-Sheng; Schwerdtfeger, Peter

    2016-06-20

    Golden fullerenes have recently been identified by photoelectron spectra by Bulusu et al. [S. Bulusu, X. Li, L.-S. Wang, X. C. Zeng, PNAS 2006, 103, 8326-8330]. These unique triangulations of a sphere are related to fullerene duals having exactly 12 vertices of degree five, and the icosahedral hollow gold cages previously postulated are related to the Goldberg-Coxeter transforms of C20 starting from a triangulated surface (hexagonal lattice, dual of a graphene sheet). This also relates topologically the (chiral) gold nanowires observed to the (chiral) carbon nanotubes. In fact, the Mackay icosahedra well known in gold cluster chemistry are related topologically to the dual halma transforms of the smallest possible fullerene C20 . The basic building block here is the (111) fcc sheet of bulk gold which is dual to graphene. Because of this interesting one-to-one relationship through Euler's polyhedral formula, there are as many golden fullerene isomers as there are fullerene isomers, with the number of isomers Niso increasing polynomially as O(Niso9 ). For the recently observed Au16- , Au17- , and Au18- we present simulated photoelectron spectra including all isomers. We also predict the photoelectron spectrum of Au32- . The stability of the golden fullerenes is discussed in relation with the more compact structures for the neutral and negatively charged Au12 to Au20 and Au32 clusters. As for the compact gold clusters we observe a clear trend in stability of the hollow gold cages towards the (111) fcc sheet. The high stability of the (111) fcc sheet of gold compared to the bulk 3D structure explains the unusual stability of these hollow gold cages. PMID:27244703

  2. Regioselective placement of alkanethiolate domains on tetrahedral and octahedral gold nanocrystals.

    Science.gov (United States)

    Wang, Yifeng; Zeiri, Offer; Meshi, Louisa; Stellacci, Francesco; Weinstock, Ira A

    2012-10-01

    Electrostatically stabilized monolayer shells of metal-oxide cluster anions (polyoxometalates, or POMs) on the surfaces of ca. 8 nm tetrahedral and octahedral gold nanocrystals regioselectively direct water-soluble alkanethiolate ligands to the corners and edges of the gold polyhedra. PMID:22918232

  3. Hunan Gold Corporation Visiting South America to Develop Gold Resources

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>On November 2nd,Hunan Gold Corporation signed a cooperation agreement to collaboratively exploit gold resources in South America.Gold Corporation has made its first"Step Out",initiating its overseas landscape layout of resources.Gold Corporation is a leading enterprise of nonferrous metals in Hunan Province,the

  4. Well-Defined Dinuclear Gold Complexes for Preorganization-Induced Selective Dual Gold Catalysis.

    Science.gov (United States)

    Vreeken, Vincent; Broere, Daniël L J; Jans, Anne C H; Lankelma, Marianne; Reek, Joost N H; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-08-16

    The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual gold catalysis are explored. Using the preorganizing abilities of the ditopic PN(H) P(iPr) (L(H) ) ligand, dinuclear Au(I) -Au(I) complex 1 and mixed-valent Au(I) -Au(III) complex 2 provide access to structurally characterized chlorido-bridged cationic species 3 and 4 upon halide abstraction. For 2, this transformation involves unprecedented two-electron oxidation of the redox-active ligand, generating a highly rigidified environment for the Au2 core. Facile reaction with phenylacetylene affords the σ,π-activated phenylacetylide complex 5. When applied in the dual gold heterocycloaddition of a urea-functionalized alkyne, well-defined precatalyst 3 provides high regioselectivities for the anti-Markovnikov product, even at low catalyst loadings, and outperforms common mononuclear Au(I) systems. This proof-of-concept demonstrates the benefit of preorganization of two gold centers to enforce selective non-classical σ,π-activation with bifunctional substrates. PMID:27430938

  5. Gold Spiky Nanodumbbells: Anisotropy in Gold Nanostars

    OpenAIRE

    Novikov, Sergey M.; Sánchez-Iglesias, Ana; Schmidt, Mikołaj K.; Chuvilin, Andrey; Aizpurua, Javier; Grzelczak, Marek; Liz-Marzán, Luis M.

    2013-01-01

    A new type of gold nanoparticle—called “spiky nanodumbbells”—is introduced. These particles combine the anisotropy of nanorods with sharp nanoscale features of nanostars, which are important for SERS applications. Both the morphology and the optical response of the particles are characterized in detail, and the experimental results are compared with FDTD simulations, showing good agreement.

  6. Cationic speciation in nonaqueous media

    International Nuclear Information System (INIS)

    Electronic spectra of solutions of d transition elements in the superacids HF, H2SO4, HSO3F, and CF3SO3H and in chloroaluminate melts indicate that in acidic monaqueous media the elements are present as solvated cations, whereas in basic media the speciation is anionic, the same situation as in aqueous solutions. Further, in very highly acidic media, cations in very low oxidation states are stable (e.g., Ti2+), but these disproportionate on addition of base to the system. In this paper spectra, where available, of U, Np, and Pu in oxidation states III and IV in aqueous media, in protonic superacids, and in chloroaluminates are presented to postulate cationic speciation of these early actinides in highly acidic media

  7. Gold und Peanuts

    OpenAIRE

    Hashmi, Stephen

    2003-01-01

    Die bisherigen Kenntnisse zur Gold-Katalyse lassen sich wie folgt zusammenfassen: 1. Gold-Katalysatoren reagieren rasch mit Kohlenstoff-Kohlenstoff-Mehrfachbindungen und sind somit besonders für einen Einsatz in der Organischen Chemie,der Chemie des Kohlenstoffs, geeignet. Dies lässt sich damit erklären, dass Gold und Kohlenstoff gemäß des Prinzips der harten und weichen Säuren und Basen („hard and soft acids and bases“, HSABPrinzip)beide als „weich“ klassifiziert werden und dieses Prinzi...

  8. Two gold return puzzles

    OpenAIRE

    Kolev, Gueorgui I.

    2013-01-01

    Since the dismantling of the Bretton Woods system, gold has delivered average return comparable to the average return delivered by the aggregate US stock market. This suggests that none of the growth and technological improvement gains accrued to the financiers. In the context of modern asset pricing models, say the CAPM model or the Fama-French three factor model, gold is a risk free asset, as it has no covariation with the risk factors. The large average gold return is a Jensen's alpha not ...

  9. Chiseled Gold Ornament

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    According to some archaeological discoveries, people began to use gold to make ornaments during the Shang Dynasty, more than 3,000 years ago. This partfcular piece of chiseled gold ornament was unearthed in 1957 from the Ming Dynasty tomb of Wang Gui at You’anmen, Beijing. Wang Gui was a head of the Imperial Bodyguard in the Ming Dynasty. His eldest daughter was an imperial concubine of the Emperor Cheng Hua. Consequently, his family held a prominent position at the time. The gold ornament, 50.5 centimeters in length and 295 grams in weight, is composed of two parts. The upper part is shaped like lotus leaves, with fine double lines as the vein. To indicate auspiciousness, a pair of mandarin ducks with lotus flowers in their months sit on either side of the thick leaves. Seven long gold chains measuring 21 centimeters in length link the

  10. Paying twice for Gold

    OpenAIRE

    Ayris, P.

    2014-01-01

    EU governments seem to prefer gold in the debate on Open Access. The problem with ‘gold’ is that often subscription fees for universities persist while authors now pay too. The League of European Research Universities raises critical questions.

  11. Electrolytic refining of gold

    OpenAIRE

    Wohlwill, Emil

    2008-01-01

    At the request of the editor of ELECTROCHEMICAL INDUSTRY, I herewith give some notes on the electrolytic method of gold refining, to supplement the article of Dr. Tuttle (Vol. I, page 157, January, 1903).

  12. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  13. The Gold Standard Programme

    DEFF Research Database (Denmark)

    Neumann, Tim; Rasmussen, Mette; Ghith, Nermin;

    2013-01-01

    To evaluate the real-life effect of an evidence-based Gold Standard Programme (GSP) for smoking cessation interventions in disadvantaged patients and to identify modifiable factors that consistently produce the highest abstinence rates.......To evaluate the real-life effect of an evidence-based Gold Standard Programme (GSP) for smoking cessation interventions in disadvantaged patients and to identify modifiable factors that consistently produce the highest abstinence rates....

  14. Joining the Gold Rush

    Institute of Scientific and Technical Information of China (English)

    LIU BO

    2006-01-01

    @@ Flush with advanced technology and large amounts of capital, overseas mining firms are carving a place in the Chinese gold industry Dozens of Western mining companies, particularly those from Canada, are making the journey into the kind of remote corners in China that other overseas investors shy away from. What are they looking for? The answer is one of the most precious substances on the planet: gold.

  15. Gold induced enterocolitis.

    OpenAIRE

    Jackson, C W; Haboubi, N Y; Whorwell, P.J.; Schofield, P. F.

    1986-01-01

    A case of gold associated enterocolitis is described. A review of all 27 previously reported cases revealed that the syndrome induced has common characteristics. The reaction occurs within three months of instituting gold therapy, is characterised by profuse diarrhoea and vomiting with abdominal pain, fever, and sometimes eosinophilia. Petechial changes are prominent on endoscopy and the endoscopic and histological features of the gut lesion do not resemble inflammatory bowel disease. The ove...

  16. Gold prices and inflation

    OpenAIRE

    Tkacz, Greg

    2007-01-01

    Using data for 14 countries over the 1994 to 2005 period, we assess the leading indicator properties of gold at horizons ranging from 6 to 24 months. We find that gold contains significant information for future inflation for several countries, especially for those that have adopted formal inflation targets. This finding may arise from the manner in which inflation expectations are formed in these countries, which may result in more rapidly mean-reverting inflation rates. Compared to other in...

  17. Gold or Penicillamine?

    OpenAIRE

    Offer, R. C.

    1981-01-01

    The recent approval of penicillamine (Cupramine) for use in rheumatoid arthritis has given the physician another remission-inducing drug for this disease. A thorough understanding of penicillamine's administration and toxicity is necessary before the physician begins to use it. Although its efficacy is similar to gold, side effects are considerably more diverse, and longterm side effects require further assessment. This article reviews the clinical use of gold and penicillamine and the factor...

  18. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  19. Screening Nylon-3 Polymers, a New Class of Cationic Amphiphiles, for siRNA Delivery

    OpenAIRE

    Nadithe, Venkatareddy; Liu, Runhui; Killinger, Bryan A.; Movassaghian, Sara; Kim, Na Hyung; Moszczynska, Anna B.; Masters, Kristyn S.; Gellman, Samuel H.; Merkel, Olivia M

    2014-01-01

    Amphiphilic nucleic acid carriers have attracted strong interest. Three groups of nylon-3 copolymers (poly-β-peptides) possessing different cationic/hydrophobic content were evaluated as siRNA delivery agents in this study. Their ability to condense siRNA was determined in SYBR Gold assays. Their cytotoxicity was tested by MTT assays, their efficiency of delivering Alexa Fluor-488-labeled siRNA intracellularly in the presence and absence of uptake inhibitors was assessed by flow cytometry, an...

  20. Cluster emission under femtosecond laser ablation of silicon

    OpenAIRE

    Bulgakov, Alexander,; Ozerov, Igor; Marine, Wladimir

    2003-01-01

    Rich populations of clusters have been observed after femtosecond laser ablation of bulk silicon in vacuum. Size and velocity distributions of the clusters as well as their charge states have been analyzed by reflectron time-of-flight mass spectrometry. An efficient emission of both neutral silicon clusters Sin (up to n = 6) and their cations Sin+ (up to n = 10) has been observed. The clusters are formed even at very low laser fluences, below ablation threshold, and their relative yield incre...

  1. Weighted Clustering

    DEFF Research Database (Denmark)

    Ackerman, Margareta; Ben-David, Shai; Branzei, Simina;

    2012-01-01

    We investigate a natural generalization of the classical clustering problem, considering clustering tasks in which different instances may have different weights.We conduct the first extensive theoretical analysis on the influence of weighted data on standard clustering algorithms in both the...... partitional and hierarchical settings, characterizing the conditions under which algorithms react to weights. Extending a recent framework for clustering algorithm selection, we propose intuitive properties that would allow users to choose between clustering algorithms in the weighted setting and classify...

  2. Cluster Headache

    OpenAIRE

    Frederick G Freitag

    1985-01-01

    Learning Objectives: Review the current understanding of the pathophysiology of cluster headache Be able to recognize the clinical features of cluster headache Be able to develop a strategy for treatment of cluster headache Cluster headache is divided into multiple subtypes under the IHC classification criteria. The vast majority of patients present with episodic cluster headache (3.1.1). This will be the focus of the presentation. The syndrome is characterized by repeated at...

  3. Biosynthesis of gold nanoparticles using diatoms-silica-gold and EPS-gold bionanocomposite formation

    OpenAIRE

    Schröfel, Adam; Kratošová, Gabriela; Bohunická, Markéta; Dobročka, Edmund; Vávra, Ivo

    2011-01-01

    Novel synthesis of gold nanoparticles, EPS-gold, and silica-gold bionanocomposites by biologically driven processes employing two diatom strains (Navicula atomus, Diadesmis gallica) is described. Transmission electron microscopy (TEM) and electron diffraction analysis (SAED) revealed a presence of gold nanoparticles in the experimental solutions of the diatom culture mixed with tetrachloroaureate. Nature of the gold nanoparticles was confirmed by X-ray diffraction studies. Scanning electron m...

  4. Study of chemical processes involved in silver staining of gold nanostructures by Raman scattering

    Science.gov (United States)

    Ji, Xiaohui; Yang, Wensheng

    2016-05-01

    Strong Raman enhancement contributed by ``hot spots'' in directly fused gold dimers offer a selective and sensitive tool for understanding the surface processes involved in the silver staining of gold nanostructures. These processes include the interactions of cations, effects of surface adsorbed Cl- ions, surface replacement of ligands, and reduction of silver ions on the surface of the gold nanocrystals. Results show that in the commonly applied silver staining scheme for gold nanostructures, i.e., the addition of the Raman probe after the deposition of the silver shell, the Raman signals of the probe (p-mercaptobenzoic acid) were weakened greatly, due to the pre-existence of the Cl--Ag+-citrate bridges on the surface of the gold. A new scheme was developed for silver deposition after pre-adsorption of the probe, which achieved a Raman enhancement factor as high as ~5 × 108.Strong Raman enhancement contributed by ``hot spots'' in directly fused gold dimers offer a selective and sensitive tool for understanding the surface processes involved in the silver staining of gold nanostructures. These processes include the interactions of cations, effects of surface adsorbed Cl- ions, surface replacement of ligands, and reduction of silver ions on the surface of the gold nanocrystals. Results show that in the commonly applied silver staining scheme for gold nanostructures, i.e., the addition of the Raman probe after the deposition of the silver shell, the Raman signals of the probe (p-mercaptobenzoic acid) were weakened greatly, due to the pre-existence of the Cl--Ag+-citrate bridges on the surface of the gold. A new scheme was developed for silver deposition after pre-adsorption of the probe, which achieved a Raman enhancement factor as high as ~5 × 108. Electronic supplementary information (ESI) available: Fig. S1-S3. See DOI: 10.1039/c6nr01208f

  5. Polyelectrolyte Condensation Induced by Linear Cations

    OpenAIRE

    Guáqueta, Camilo; Luijten, Erik

    2007-01-01

    We examine the role of the condensing agent in the formation of polyelectrolyte bundles, via grand-canonical Monte Carlo simulations. Following recent experiments we use linear, rigid divalent cations of various lengths to induce condensation. Our results clarify and explain the experimental results for short cations. For longer cations we observe novel condensation behavior owing to alignment of the cations. We also study the role of the polyelectrolyte surface charge density, and find a non...

  6. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  7. Organometallic cation-exchanged phyllosilicates

    OpenAIRE

    Fleming, Shay

    1991-01-01

    Organotin (IV) complexes formed between 0 01 M dimethyltin dichloride solutions prepared at pH 2 6 and 4 0, and trimethyltin chloride prepared at pH 3 4, with Na- 119 montmori 1lonite clay have been characterised using Sn Mflssbauer spectroscopy, X-ray diffraction, thermogravimetric analysis and water sorption isotherms Following cation exchange, Mttssbauer spectroscopy identified two tin species in the dimethyltin (IV)-exchanged clay prepared at pH 2 6 A cis specie...

  8. Calorimetric study of cationic photopolymerization

    International Nuclear Information System (INIS)

    The photopolymerization of penta-erythritol tetra-glycidyl ether (initiator Degacure KI-85) was studied by a du Pont 910 type DSC. From our experimental results the following conclusions can be drawn: (1) During the cationic polymerization reaction the lifetime of the initiating centers are long compared to the lifetime of free radicals in case of radical polymerization. (2) The rate of deactivation of the initiating centers increases with increasing temperature. (author)

  9. High-Yield Synthesis and Applications of Anisotropic Gold Nanoparticles

    Science.gov (United States)

    Vigderman, Leonid

    This work will describe research directed towards the synthesis of anisotropic gold nanoparticles as well as their functionalization and biological applications. The thesis will begin by describing a new technique for the high-yield synthesis of gold nanorods using hydroquinone as a reducing agent. This addresses important limitations of the traditional nanorod synthesis including low yield of gold ions conversion to metallic form and inability to produce rods with longitudinal surface plasmon peak above 850 nm. The use of hydroquinone was also found to improve the synthesis of gold nanowires via the nanorod-seed mediated procedure developed in our lab. The thesis will next present the synthesis of novel starfruitshaped nanorods, mesorods, and nanowires using a modified nanorod-seed mediated procedure. The starfruit particles displayed increased activity as surfaceenhanced Raman spectroscopy (SERS) substrates as compared to smooth structures. Next, a method for the functionalization of gold nanorods using a cationic thiol, 16-mercaptohexadecyltrimethylammonium bromide (MTAB), will be described. By using this thiol, we were able to demonstrate the complete removal of toxic surfactant from the nanorods and were also able to precisely quantify the grafting density of thiol molecules on the nanorod surface through a combination of several analytical techniques. Finally, this thesis will show that MTABfunctionalized nanorods are nontoxic and can be taken up in extremely high numbers into cancer cells. The thesis will conclude by describing the surprising uptake of larger mesorods and nanowires functionalized with MTAB into cells in high quantities.

  10. Cluster headache

    Science.gov (United States)

    Histamine headache; Headache - histamine; Migrainous neuralgia; Headache - cluster; Horton's headache ... Doctors do not know exactly what causes cluster headaches. They ... (chemical in the body released during an allergic response) or ...

  11. Isotopic clusters

    International Nuclear Information System (INIS)

    Spectra of isotopically mixed clusters (dimers of SF6) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

  12. GOLD AS AN INVESTMENT VEHICLE

    Directory of Open Access Journals (Sweden)

    Arti Chandani

    2014-04-01

    Full Text Available Gold has been used extensively for savings, investments and consumption since ages; however the importance of the gold as an investment instruments has been much talked in the recent times. This research paper intends to find various applications of gold portfolios as an alternate asset class: the benefits of including gold to an investment portfolio have been analyzed. The results indicate that gold has performed significantly better than other assets like debt and equity in both emerging and US markets. It was noted that addition of gold to portfolios helped reduce the volatility and increase overall returns during the period 2009-12. For example, in 2008, when the U.S. equity market plunged to 36.99%, gold in fact showed returns of 5.8%. It is also observed that the inverse correlation exists between the dollar index and the gold prices helped reduce the portfolio risk as a result of diversification.

  13. Activated carbons and gold

    International Nuclear Information System (INIS)

    The literature on activated carbon is reviewed so as to provide a general background with respect to the effect of source material and activation procedure on carbon properties, the structure and chemical nature of the surface of the activated carbon, and the nature of absorption processes on carbon. The various theories on the absorption of gold and silver from cyanide solutions are then reviewed, followed by a discussion of processes for the recovery of gold and silver from cyanide solutions using activated carbon, including a comparison with zinc precipitation

  14. Weighted Clustering

    OpenAIRE

    Ackerman, Margareta; Ben-David, Shai; Branzei, Simina; Loker, David

    2012-01-01

    We investigate a natural generalization of the classical clusteringproblem, considering clustering tasks in which differentinstances may have different weights.We conduct the firstextensive theoretical analysis on the influence of weighteddata on standard clustering algorithms in both the partitionaland hierarchical settings, characterizing the conditions underwhich algorithms react to weights. Extending a recent frameworkfor clustering algorithm selection, we propose intuitiveproperties that...

  15. Meaningful Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Sanfilippo, Antonio P.; Calapristi, Augustin J.; Crow, Vernon L.; Hetzler, Elizabeth G.; Turner, Alan E.

    2004-05-26

    We present an approach to the disambiguation of cluster labels that capitalizes on the notion of semantic similarity to assign WordNet senses to cluster labels. The approach provides interesting insights on how document clustering can provide the basis for developing a novel approach to word sense disambiguation.

  16. Vibrational autodetachment spectroscopy of Au-6 : Image-charge-bound states of a gold ring

    International Nuclear Information System (INIS)

    Spectral experiments on mass-selected negative cluster ions of gold and silver were performed in the wavelength range near the threshold for one-photon photodetachment of the extra electron. The Au-6 cluster ion displayed a uniquely well resolved spectrum consisting of a progression in a single vibrational mode. Details of this threshold photodetachment spectrum and the associated photoelectron energy distribution suggest an explanation based on autodetachment from totally symmetric vibrational levels of very weakly bound excited electronic state (bound by image charge forces) of the Au-6 cluster in the form of a planar, six-fold symmetric, gold ring

  17. Adsorption of doxorubicin on citrate-capped gold nanoparticles: insights into engineering potent chemotherapeutic delivery systems

    Science.gov (United States)

    Curry, Dennis; Cameron, Amanda; MacDonald, Bruce; Nganou, Collins; Scheller, Hope; Marsh, James; Beale, Stefanie; Lu, Mingsheng; Shan, Zhi; Kaliaperumal, Rajendran; Xu, Heping; Servos, Mark; Bennett, Craig; Macquarrie, Stephanie; Oakes, Ken D.; Mkandawire, Martin; Zhang, Xu

    2015-11-01

    Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates.Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied

  18. Colloidal Synthesis of Gold Semishells

    OpenAIRE

    Rodríguez-Fernández, Denis; Rodríguez-Fernández, Denis; Pérez-Juste, Jorge; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel; Liz-Marzán, Luis M.; Liz-Marzán, Luis M.

    2012-01-01

    This work describes a novel and scalable colloid chemistry strategy to fabricate gold semishells based on the selective growth of gold on Janus silica particles (500 nm in diameter) partly functionalized with amino groups. The modulation of the geometry of the Janus silica particles allows us to tune the final morphology of the gold semishells. This method also provides a route to fabricating hollow gold semishells through etching of the silica cores with hydrofluoric acid. The optical proper...

  19. Nanocomposite gold-silk nanofibers

    OpenAIRE

    Cohen-Karni, Tzahi; Jeong, Kyung Jae; Tsui, Jonathan H.; Reznor, Gally; Mustata, Mirela; Wanunu, Meni; Graham, Adam; Marks, Carolyn; Bell, David C.; Langer, Robert S; Kohane, Daniel S.

    2012-01-01

    Cell-biomaterial interactions can be controlled by modifying the surface chemistry or nanotopography of the material, to induce cell proliferation and differentiation if desired. Here we combine both approaches in forming silk nanofibers (SNFs) containing gold nanoparticles (AuNPs) and subsequently chemically modifying the fibers. Silk fibroin mixed with gold seed nanoparticles was electrospun to form SNFs doped with gold seed nanoparticles (SNFseed). Following gold reduction, there was a two...

  20. Influence of α-amylase template concentration on systematic entrapment of highly stable and monodispersed colloidal gold nanoparticles

    OpenAIRE

    A. Nitthin Ananth; A. Nimrodh Ananth; Sujin P. Jose; Umapathy, S.; T. Mathavan

    2016-01-01

    Nano gold / α-amylase colloidal dispersions of profound stability were made using simple procedure with a conventional reducing agent. The surface plasmon resonance of the gold nanocrystals was used to quantify the extent of the dispersion stability and functionalization. It is found that the reduced gold nanoparticles were trapped into the protein network without denaturation the structure of α-amylase protein. This kind of entrapment of particles into the protein network prevents clustering...

  1. Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

    Science.gov (United States)

    Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

    2016-04-20

    The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation. PMID:26762578

  2. ['Gold standard', not 'golden standard'

    NARCIS (Netherlands)

    Claassen, J.A.H.R.

    2005-01-01

    In medical literature, both 'gold standard' and 'golden standard' are employed to describe a reference test used for comparison with a novel method. The term 'gold standard' in its current sense in medical research was coined by Rudd in 1979, in reference to the monetary gold standard. In the same w

  3. Processing Gold Quarry refractory ores

    Science.gov (United States)

    Hausen, D. M.

    1989-04-01

    The Gold Quarry deposit is the largest sediment-hosted gold deposit yet discovered on the Carlin trend in northern Nevada. However, despite the locale's vast reserves, the gold is difficult to extract from portions of the deposit. Detailed, ongoing mineralogical analyses assure proper treatment of the ore.

  4. Gold extraction from flotation tailings

    International Nuclear Information System (INIS)

    The results of studies on cyanide leaching of gold comprising flotation tailings of antimony ore are given. The possibility to extract 50% of gold by cyanide leaching is shown. The dependence of gold extraction on leaching duration is studied. Influence of kerosine on cyanide leaching of flotation tailings is studied as well.

  5. Photoinduced conductivity of a porphyrin-gold composite nanowire

    Energy Technology Data Exchange (ETDEWEB)

    Kilina, Svletana [Los Alamos National Laboratory; Balatsky, Alexander [Los Alamos National Laboratory; Kilin, Dmitri S [UNIV OF FL; Prezhdo, Oleg [UNIV OF WASHINGTON; Tsemekhman, Kiril [NON LANL

    2009-01-01

    Negatively charged phosphine groups on the backbone of DNA are known to attract gold nanoclusters from a colloid, assembling the clusters at fixed intervals. Bridging these intervals with porphyrin-dye linkers forms an infinite conducting chain, a quantum wire whose carrier mobility can be enhanced by photoexcitation. The resulting nanoassembly can be used as a gate: a wire with a controllable conductivity. The electronic structure of the porphyrin-gold wire is studied here by density functional theory, and the conductivity of the system is determined as a function of the photoexcitation energy. Photoexcitations of the dye are found to enhance the wire conductivity by orders of magnitude.

  6. Optical properties of gold colloids formed in inverse micelles

    International Nuclear Information System (INIS)

    We discuss the formation of gold metal colloids in a variety of surfactant/solvent systems. Static and dynamic light scattering, small angle x-ray and neutron scattering, TEM analysis, and UV-visible absorbance are used to characterize the kinetics of formation and final colloid stability. These gold colloids exhibit a dramatic blueshift and broadening of the plasmon resonance with decreasing colloid size. Several types of reduction method are discussed and differences between micelle (water-free) or microemulsions as reaction media are compared. Use of inverse micelles allows smaller clusters to be formed with greater long-term stability

  7. Visibility graph network analysis of gold price time series

    Science.gov (United States)

    Long, Yu

    2013-08-01

    Mapping time series into a visibility graph network, the characteristics of the gold price time series and return temporal series, and the mechanism underlying the gold price fluctuation have been explored from the perspective of complex network theory. The network degree distribution characters, which change from power law to exponent law when the series was shuffled from original sequence, and the average path length characters, which change from L∼lnN into lnL∼lnN as the sequence was shuffled, demonstrate that price series and return series are both long-rang dependent fractal series. The relations of Hurst exponent to the power-law exponent of degree distribution demonstrate that the logarithmic price series is a fractal Brownian series and the logarithmic return series is a fractal Gaussian series. Power-law exponents of degree distribution in a time window changing with window moving demonstrates that a logarithmic gold price series is a multifractal series. The Power-law average clustering coefficient demonstrates that the gold price visibility graph is a hierarchy network. The hierarchy character, in light of the correspondence of graph to price fluctuation, means that gold price fluctuation is a hierarchy structure, which appears to be in agreement with Elliot’s experiential Wave Theory on stock price fluctuation, and the local-rule growth theory of a hierarchy network means that the hierarchy structure of gold price fluctuation originates from persistent, short term factors, such as short term speculation.

  8. Cation coordination in oxychloride glasses

    Science.gov (United States)

    Johnson, J. A.; Holland, D.; Bland, J.; Johnson, C. E.; Thomas, M. F.

    2003-02-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Mössbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2].

  9. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Glasses containing mixtures of cations and anions of nominal compositions [Sb2O3]x - [ZnCl2]1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb)2(OZn)] and [Zn(ClZn)2(OSb)2

  10. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  11. Turning lead into gold

    DEFF Research Database (Denmark)

    Jensen, Steffen Moltrup Ernø

    For years the field of entrepreneurship has been blinded by the alchemical promise of turning lead into gold, of finding the ones most likely to become the next Branson, Zuckerberg or Gates. The promise has been created in the midst of political and scientific agendas where certain individuals, the...

  12. Gold Nanoparticle Microwave Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Krantz, Kelsie E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Christian, Jonathan H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Coopersmith, Kaitlin [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Washington, II, Aaron L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Murph, Simona H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-07-27

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves for gold nanoparticle synthesis; however polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, a reduction in reaction time from 10 minutes to 1 minute, maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.

  13. Digging for Gold

    Science.gov (United States)

    Waters, John K.

    2012-01-01

    In the case of higher education, the hills are more like mountains of data that "we're accumulating at a ferocious rate," according to Gerry McCartney, CIO of Purdue University (Indiana). "Every higher education institution has this data, but it just sits there like gold in the ground," complains McCartney. Big Data and the new tools people are…

  14. Aiming for Gold

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Twenty-three years ago he claimed China’s first Olympic gold medal,with a win in the 50-meter pistol shooting competition.Now Xu Haifeng is leading the country’s modern pentathlon team in its bid for success at the Beijing Games

  15. Gold Nanoslit Lenses

    OpenAIRE

    Ishii, Satoshi; Kildishev, Alexander V.; Shalaev, Vladimir M.; Chen, Kuo-Ping; Drachev, Vladimir P.

    2011-01-01

    We experimentally demonstrate the focusing properties of arrays of parallel subwavelength-wide nanoslits in a gold film. The lenses are designed to focus either TM- or TE-polarized light and diverge the light of the orthogonal polarization. (C) 2010 Optical Society of America

  16. Gold in Ophiolites

    OpenAIRE

    Castroviejo Bolibar, Ricardo

    2004-01-01

    Ophiolites, as a class, have been currently under-estimated as potential gold targets, although they have been the subject of major scientific research. Their resources have also attracted investors producing Cr, Cu (massive sulphides), Co, Ni (laterites), industrial rocks and minerals (serpentinites, emeralds), etc. They are also potential PGE sources.

  17. Gold trifluoromethyl complexes.

    Science.gov (United States)

    Gil-Rubio, Juan; Vicente, José

    2015-12-01

    This article reviews the synthesis, reactivity and applications of gold trifluoromethyl complexes, which are the only isolated perfluoroalkyl complexes of gold. The most reported examples are neutral Au(i) complexes of the type [Au(CF3)L], whereas only two Au(ii) trifluoromethyl complexes have been reported, both being diamagnetic and containing a strong Au-Au bond. A number of Au(iii) trifluoromethyl complexes have been prepared by oxidative addition of halogens or iodotrifluoromethane to Au(i) complexes or, in a few cases, by transmetallation reactions. Owing to the limitations of the available synthetic methods, a lower number of examples is known, particularly for the oxidation states (ii) and (iii). Gold trifluoromethyl complexes present singular characteristics, such as thermal stability, strong Au-C bonds and, in some cases, reactive α-C-F bonds. Some of the Au(iii) complexes reported, show unusually easy reductive elimination reactions of trifluoromethylated products which could be applied in the development of gold-catalyzed processes for the trifluoromethylation of organic compounds. PMID:26169553

  18. Cluster Lenses

    CERN Document Server

    Kneib, Jean-Paul; 10.1007/s00159-011-0047-3

    2012-01-01

    Clusters of galaxies are the most recently assembled, massive, bound structures in the Universe. As predicted by General Relativity, given their masses, clusters strongly deform space-time in their vicinity. Clusters act as some of the most powerful gravitational lenses in the Universe. Light rays traversing through clusters from distant sources are hence deflected, and the resulting images of these distant objects therefore appear distorted and magnified. Lensing by clusters occurs in two regimes, each with unique observational signatures. The strong lensing regime is characterized by effects readily seen by eye, namely, the production of giant arcs, multiple-images, and arclets. The weak lensing regime is characterized by small deformations in the shapes of background galaxies only detectable statistically. Cluster lenses have been exploited successfully to address several important current questions in cosmology: (i) the study of the lens(es) - understanding cluster mass distributions and issues pertaining...

  19. Use of laser induced photoacoustic spectroscopy (LIPAS) to determine equilibrium constants of cation-cation complexes

    International Nuclear Information System (INIS)

    Laser Induced PhotoAcoustic Spectroscopy (LIPAS) is a relatively new, photothermal technique to examine solutions. Studies in the past have shown it to be more sensitive than conventional absorption spectroscopy, while, yielding the same information thus allowing lower concentrations to be used. This study is using LIPAS to examine solutions to determine the equilibrium constants of cation-cation complexes. It has been found that actinyl(V) cations form cation-cation complexes with a variety of cations, including actinyl(VI) cations. The radioactive nature of the actinide elements requires special handling techniques and also require limits be placed on the amount of material that can be used. The sensitivity of some oxidation states of the actinides to oxygen also presents a problem. Preliminary results will be presented for actinyl(V)-actinyl(VI) cation-cation complexes that were studied using a remote LIPAS system incorporating fiber optics for transmission of laser signals

  20. Evidence of energy transfer from tryptophan to BSA/HSA protected gold nanoclusters

    International Nuclear Information System (INIS)

    This work reports on the chromophores interactions within protein-protected gold nanoclusters. We conducted spectroscopic studies of fluorescence emissions originated from gold nanoclusters and intrinsic tryptophan (Trp) in BSA or HSA proteins. Both steady state fluorescence and lifetime measurements showed a significant Forster Resonance Energy Transfer (FRET) from Trp to the gold nanocluster. Tryptophan lifetimes in the case of protein-protected gold nanoclusters are 2.6 ns and 2.3 ns for BSA and HSA Au clusters while 5.8 ns for native BSA and 5.6 for native HSA. The apparent distances from Trp to gold nanocluster emission center, we estimated as 24.75 Å for BSA and 23.80 Å for HSA. We also studied a potassium iodide (KI) quenching of protein-protected gold nanoclusters and compared with the quenching of BSA and HSA alone. The rates of Trp quenching were smaller in BSA-Au and HSA-Au nanoclusters than in the case of free proteins, which is consistent with shorter lifetime of quenched Trp(s) and lower accessibility for KI. While Trp residues were quenched by KI, the emissions originated from nanoclusters were practically unquenched. In summary, for BSA and HSA Au clusters, we found 55% and 59% energy transfer efficiency respectively from tryoptophan to gold clusters. We believe this interaction can be used to our advantage in terms of developing resonance energy transfer based sensing applications. (paper)

  1. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  2. Bosonic helium droplets with cationic impurities: Onset of electrostriction and snowball effects from quantum calculations

    International Nuclear Information System (INIS)

    Variational Monte Carlo and diffusion Monte Carlo calculations have been carried out for cations such as Li+, Na+, and K+ as dopants of small helium clusters over a range of cluster sizes up to about 12 solvent atoms. The interaction has been modeled through a sum-of-potential picture that disregards higher order effects beyond atom-atom and atom-ion contributions. The latter were obtained from highly correlated ab initio calculations over a broad range of interatomic distances. This study focuses on two of the most striking features of the microsolvation in a quantum solvent of a cationic dopant: electrostriction and snowball effects. They are discussed here in detail and in relation with the nanoscopic properties of the interaction forces at play within a fully quantum picture of the cluster features

  3. Bosonic Helium droplets with cationic impurities: onset of electrostriction and snowball effects from quantum calculations

    CERN Document Server

    Coccia, E; Marinetti, F; Gianturco, F A; Yildrim, E; Yurtsever, M; Yurtsever, E

    2007-01-01

    Variational MonteCarlo and Diffusion MonteCarlo calculations have been carried out for cations like Li$^+$, Na$^+$ and K$^+$ as dopants of small helium clusters over a range of cluster sizes up to about 12 solvent atoms. The interaction has been modelled through a sum-of-potential picture that disregards higher order effects beyond atom-atom and atom-ion contributions. The latter were obtained from highly correlated ab-initio calculations over a broad range of interatomic distances. This study focuses on two of the most striking features of the microsolvation in a quantum solvent of a cationic dopant: electrostriction and snowball effects. They are here discussed in detail and in relation with the nanoscopic properties of the interaction forces at play within a fully quantum picture of the clusters features.

  4. Growth mechanisms for doped clusters

    International Nuclear Information System (INIS)

    Structural growth mechanisms for metal doped nanoclusters are investigated in combined experimental and theoretical studies. In particular, silicon, copper and gold clusters incorporating a transition metal dopant atom are investigated: SinX (X=Cu, V), CunSc+ and AunY+ with n < 20. The doped clusters are produced with a dual-target dual-laser vaporization source. Structural information about the doped nanoclusters is provided by infrared multi-photon dissociation spectroscopy. Their size and composition dependent stability is studied with photofragmentation and mass spectrometry. A detailed understanding of the role of the dopant atom in the structural growth and in the electronic structure of the clusters is obtained by comparison with quantum chemical computations using density functional theory. (review)

  5. Anti-inflammatory activity of cationic lipids

    OpenAIRE

    Filion, Mario C; Phillips, Nigel C

    1997-01-01

    The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids.We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-α (TNF-α).In this study, we have evaluated the ability of different cationic lipids to reduce footpad inf...

  6. Data Clustering

    Science.gov (United States)

    Wagstaff, Kiri L.

    2012-03-01

    On obtaining a new data set, the researcher is immediately faced with the challenge of obtaining a high-level understanding from the observations. What does a typical item look like? What are the dominant trends? How many distinct groups are included in the data set, and how is each one characterized? Which observable values are common, and which rarely occur? Which items stand out as anomalies or outliers from the rest of the data? This challenge is exacerbated by the steady growth in data set size [11] as new instruments push into new frontiers of parameter space, via improvements in temporal, spatial, and spectral resolution, or by the desire to "fuse" observations from different modalities and instruments into a larger-picture understanding of the same underlying phenomenon. Data clustering algorithms provide a variety of solutions for this task. They can generate summaries, locate outliers, compress data, identify dense or sparse regions of feature space, and build data models. It is useful to note up front that "clusters" in this context refer to groups of items within some descriptive feature space, not (necessarily) to "galaxy clusters" which are dense regions in physical space. The goal of this chapter is to survey a variety of data clustering methods, with an eye toward their applicability to astronomical data analysis. In addition to improving the individual researcher’s understanding of a given data set, clustering has led directly to scientific advances, such as the discovery of new subclasses of stars [14] and gamma-ray bursts (GRBs) [38]. All clustering algorithms seek to identify groups within a data set that reflect some observed, quantifiable structure. Clustering is traditionally an unsupervised approach to data analysis, in the sense that it operates without any direct guidance about which items should be assigned to which clusters. There has been a recent trend in the clustering literature toward supporting semisupervised or constrained

  7. Selective Gold Recovery and Catalysis in a Highly Flexible Methionine-Decorated Metal-Organic Framework.

    Science.gov (United States)

    Mon, Marta; Ferrando-Soria, Jesús; Grancha, Thais; Fortea-Pérez, Francisco R; Gascon, Jorge; Leyva-Pérez, Antonio; Armentano, Donatella; Pardo, Emilio

    2016-06-29

    A novel chiral 3D bioMOF exhibiting functional channels with thio-alkyl chains derived from the natural amino acid l-methionine (1) has been rationally prepared. The well-known strong affinity of gold for sulfur derivatives, together with the extremely high flexibility of the thioether "arms" decorating the channels, account for a selective capture of gold(III) and gold(I) salts in the presence of other metal cations typically found in electronic wastes. The X-ray single-crystal structures of the different gold adsorbates Au(III)@1 and Au(I)@1 suggest that the selective metal capture occurs in a metal ion recognition process somehow mimicking what happens in biological systems and protein receptors. Both Au(III)@1 and Au(I)@1 display high activity as heterogeneous catalyst for the hydroalkoxylation of alkynes, further expanding the application of these novel hybrid materials. PMID:27295383

  8. Innovative preparation of Au/C by replication of gold-containing mesoporous silica catalysts

    KAUST Repository

    Kerdi, Fatmé

    2010-01-01

    A new strategy, based on the nanocasting concept, has been used to prepare gold nanoparticles (NPs) highly dispersed in meso-structured carbons. Gold is first introduced in various functionalized mesostructured silicas (MCM-48 and SBA-15) and particles are formed inside the porosity upon reduction of Au 3+ cations. Silica pores are then impregnated with a carbon precursor and the composite material is heated at 900°C under vacuum. Silica is then removed by acid leaching, leading to partially encapsulated gold particles in mesoporous carbon. Carbon prevents aggregation of gold particles at high temperature, both the mean size and distribution being similar to those observed in silica. However, while Au@SiO2 exhibit significant catalytic activity in the aerobic oxidation of trans-stilbene in the liquid phase, its Au@C mesostructured replica is quite inactive. © 2010 Elsevier B.V. All rights reserved.

  9. The global k-means clustering algorithm

    OpenAIRE

    Likas, Aristidis; Vlassis, Nikos; Verbeek, Jakob

    2003-01-01

    We present the global k-means algorithm which is an incremental approach to clustering that dynamically adds one cluster center at a time through a deterministic global search procedure consisting of N (with N being the size of the data set) executions of the k-means algorithm from suitable initial positions. We also propose modi2cations of the method to reduce the computational load without signi2cantly a3ecting solution quality. The proposed clustering methods are tested on well-known data ...

  10. Anti-inflammatory activity of cationic lipids.

    Science.gov (United States)

    Filion, M C; Phillips, N C

    1997-10-01

    1. The effect of liposome phospholipid composition has been assumed to be relatively unimportant because of the presumed inert nature of phospholipids. 2. We have previously shown that cationic liposome formulations used for gene therapy inhibit, through their cationic component, the synthesis by activated macrophages of the pro-inflammatory mediators nitric oxide (NO) and tumour necrosis factor-alpha (TNF-alpha). 3. In this study, we have evaluated the ability of different cationic lipids to reduce footpad inflammation induced by carrageenan and by sheep red blood cell challenge. 4. Parenteral (i.p. or s.c) or local injection of the positively charged lipids dimethyldioctadecylammomium bromide (DDAB), dioleyoltrimethylammonium propane (DOTAP), dimyristoyltrimethylammonium propane (DMTAP) or dimethylaminoethanecarbamoyl cholesterol (DC-Chol) significantly reduced the inflammation observed in both models in a dose-dependent manner (maximum inhibition: 70-95%). 5. Cationic lipids associated with dioleyol- or dipalmitoyl-phosphatidylethanolamine retained their anti-inflammatory activity while cationic lipids associated with dipalmitoylphosphatidylcholine (DPPC) or dimyristoylphosphatidylglycerol (DMPG) showed no anti-inflammatory activity, indicating that the release of cationic lipids into the macrophage cytoplasm is a necessary step for anti-inflammatory activity. The anti-inflammatory activity of cationic lipids was abrogated by the addition of dipalmitoylphosphatidylethanolamine-poly(ethylene)glycol-2000 (DPPE-PEG2000) which blocks the interaction of cationic lipids with macrophages. 6. Because of the significant role of protein kinase C (PKC) in the inflammatory process we have determined whether the cationic lipids used in this study inhibit PKC activity. The cationic lipids significantly inhibited the activity of PKC but not the activity of a non-related protein kinase, PKA. The synthesis of interleukin-6 (IL-6), which is not dependent on PKC activity for its

  11. Magnetic anisotropies of late transition metal atomic clusters

    OpenAIRE

    Fernández-Seivane, Lucas; Ferrer, Jaime

    2006-01-01

    We analyze the impact of the magnetic anisotropy on the geometric structure and magnetic ordering of small atomic clusters of palladium, iridium, platinum and gold, using Density Functional Theory. Our results highlight the absolute need to include self-consistently the spin orbit interaction in any simulation of the magnetic properties of small atomic clusters, and a complete lack of universality in the magnetic anisotropy of small-sized atomic clusters.

  12. Cluster Chemistry

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.

  13. The Financial Economics of Gold - a survey

    OpenAIRE

    O'Connor, Fergal; Lucey, Brian; Batten, Jonathan; Baur, Dirk

    2015-01-01

    We review the literature on gold as an investment. We summarize a wide variety of literature. We begin with a review of how the gold markets operate, including the under researched leasing market; we proceed to examine research on physical gold demand and supply, gold mine economics and move onto analyses of gold as an investment. Additional sections provide context on gold market efficiency, the issue of gold market bubbles, gold’s relation to inflation and interest rates, and the very na...

  14. Magnetron sputtering cluster apparatus for formation and deposition of size-selected metal nanoparticles

    DEFF Research Database (Denmark)

    Hanif, Muhammad; Popok, Vladimir

    The experimental setup utilizing a DC magnetron sputtering source for production of metal clusters, their size (mass) selection and following deposition in high vacuum is described. The source is capable to form clusters of various metals, for example, copper, silver, gold etc. Cluster size...... capability in formation of supported size-selected metal nanoparticles with controllable coverage for various practical applications....

  15. π Activation of Alkynes in Homogeneous and Heterogeneous Gold Catalysis.

    Science.gov (United States)

    Bistoni, Giovanni; Belanzoni, Paola; Belpassi, Leonardo; Tarantelli, Francesco

    2016-07-14

    The activation of alkynes toward nucleophilic attack upon coordination to gold-based catalysts (neutral and positively charged gold clusters and gold complexes commonly used in homogeneous catalysis) is investigated to elucidate the role of the σ donation and π back-donation components of the Au-C bond (where we consider ethyne as prototype substrate). Charge displacement (CD) analysis is used to obtain a well-defined measure of σ donation and π back-donation and to find out how the corresponding charge flows affect the electron density at the electrophilic carbon undergoing the nucleophilic attack. This information is used to rationalize the activity of a series of catalysts in the nucleophilic attack step of a model hydroamination reaction. For the first time, the components of the Dewar-Chatt-Duncanson model, donation and back-donation, are put in quantitative correlation with the kinetic parameters of a chemical reaction. PMID:27119994

  16. The RHIC gold rush

    CERN Document Server

    Schäfer, T

    2003-01-01

    Physicists are colliding gold nuclei to recreate the fireball that existed in the very early universe, and they may have found evidence for quark-gluon plasma. What happens to ordinary matter as you heat it to higher and higher temperatures, or compress it to greater and greater densities? This simple question underpins a major effort to create extreme conditions in the lab, which has recently taken the shape of the Relativistic Heavy Ion Collider (RHIC). This machine has been colliding gold nuclei since 2000, and has produced tantalizing hints that a new state of matter - the quark-gluon plasma - is created in the reactions. But it has also sparked surprises that are sending researchers back to the drawing board. (U.K.)

  17. Gold ore sorting

    International Nuclear Information System (INIS)

    Apparatus for sorting lumps of gold-bearing ore according to their gold content is described. It includes means for irradiating the lumps of ore with neutrons, e.g. a neutron tube adapted to produce at least 1010 neutrons per second with an energy of less than 4.5 MeV. The resulting intensity of 297 keV gamma rays arising from the nuclear reaction 197Au(n,n'#betta#) 197Au is measured. The measured gamma ray intensity from a given lump of ore is used to sort that lump of ore from other lumps. The apparatus includes various cylinders and a vibrator for presenting the lumps of ore to the neutrons in a geometrical configuration such as to enable the lumps to be irradiated uniformly. (author)

  18. Gold' 82 - technical sessions

    International Nuclear Information System (INIS)

    Sulphur-isotope studies had been applied by Dr. I. Lambert to a number of deposits in Western Australia and also to certain samples from Vubachickwe and other deposits in Zimbabwe. A study of the sulphur isotopes at the Dickenson Mine, revealed a wide spread of values in the mineralised zones. Metamorphic processes were likely to be significant in the concentration of gold. The iron formations at the Old Jardine Mine had been unfolded by Dr. W.S. Hallager and the pattern of sedimentation was unraveled. A gold-rich zone was separated by a barren gap from the other part of the mineralised zone. Research was also done on the effects of the metamorphic processes, and the ages of mineralisation

  19. Gold induced apoptsis study

    DEFF Research Database (Denmark)

    Laustsen, Christoffer

    2008-01-01

    Introduction   Cancer cells are highly thermo sensitive. On the basis of an article in Nature the idea arose, for a new non-invasive thermotherapy technique, based on radio frequency inductive heating of nano gold particles in an MR-scanner. Thermotherapy is getting considerably attention at the...... moment, especially in the fields of lasers, they though have some problems concerning the placement of the tumor in the human body. Local heating by MR has tremendous advance in comparison too lasers. The first step is to validate the hypothesis of the inductive heating of the gold nano particles trough...... a macrophage cell lines and automated image processing.   Results   Cell apoptosis study Three successful CSLM counters were constructed and one unsuccessful AMG counter were constructed for automated processing and counting. One successful sorting macro were also constructed for easy directory...

  20. Rushing for gold

    DEFF Research Database (Denmark)

    Jønsson, Jesper Bosse; Bryceson, Deborah Fahy

    2009-01-01

    African rural dwellers have faced depressed economic prospects for several decades. Now, in a number of mineral-rich countries, multiple discoveries of gold and precious stones have attracted large numbers of prospective small-scale miners. While their 'rush' to, and activities within, mining sit...... more affluent than the others, suggesting that movement can be rewarding for those willing to 'try their luck' with the hard work and social networking demands of mining another site.......African rural dwellers have faced depressed economic prospects for several decades. Now, in a number of mineral-rich countries, multiple discoveries of gold and precious stones have attracted large numbers of prospective small-scale miners. While their 'rush' to, and activities within, mining sites...

  1. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  2. Film Ace Takes Gold

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    "Really, I never, never expected to win this," said Chinese director Jia Zhangke on hearing he had taken the top award for his movie Still Life (Sanxia Haoren) at the Venice Film Festival, on September 9. A surprise late entry, Still Life quickly emerged as the favorite and the Gold Lion was again hugged by Chinese. The well-known Chinese director Zhang Yimou won the same award back in 1999, for Not One Less-also a

  3. Multishelled Gold Nanowires

    OpenAIRE

    Bilalbegovic, G.

    1999-01-01

    The current miniaturization of electronic devices raises many questions about the properties of various materials at nanometre-scales. Recent molecular dynamics computer simulations have shown that small finite nanowires of gold exist as multishelled structures of lasting stability. These classical simulations are based on a well-tested embedded atom potential. Molecular dynamics simulation studies of metallic nanowires should help in developing methods for their fabrication, such as electron...

  4. Gold, Oil, and Stocks

    OpenAIRE

    Baruník, Jozef; Kočenda, Evžen; Vácha, Lukáš

    2014-01-01

    We employ a wavelet approach and conduct a time-frequency analysis of dynamic correlations between pairs of key traded assets (gold, oil, and stocks) covering the period from 1987 to 2012. The analysis is performed on both intra-day and daily data. We show that heterogeneity in correlations across a number of investment horizons between pairs of assets is a dominant feature during times of economic downturn and financial turbulence for all three pairs of the assets under research. Heterogenei...

  5. Gold based electro catalysts

    OpenAIRE

    Sivasubramaniam, Prabalini

    2011-01-01

    Gold electrocatalysts have been of growing interest in recent years owing to their reactivity for a variety of important reactions such as the oxygen reduction reaction. This activity has been shown to be dependent on the size of the supported electrocatalyst nanoparticles. In this thesis the effects of Au nanoparticle size are explored for the oxygen reduction, ethanol oxidation and carbon monoxide oxidation reactions (Chapter four). The results show the oxygen reduction and ethanol oxidatio...

  6. A nonenzymatic biosensor based on gold electrodes modified with peptide self-assemblies for detecting ammonia and urea oxidation.

    Science.gov (United States)

    Bianchi, Roberta C; da Silva, Emerson Rodrigo; Dall'Antonia, Luiz H; Ferreira, Fabio Furlan; Alves, Wendel Andrade

    2014-09-30

    We have developed a nonenzymatic biosensor for the detection of ammonia and urea oxidation based on the deposition of peptide microstructures onto thiolated gold electrodes. FF-MNSs/MCP/Au assemblies were obtained by modifying gold substrates with 4-mercaptopyridine (MCP), followed by coating with l,l-diphenylalanine micro/nanostructures (FF-MNSs) grown in the solid-vapor phase. Benzene rings and amide groups with peptide micro/nanostructures interact with synthetic NH4(+) receptors through cation-π and hydrogen bonding. AuOH clusters on the Au surface provided the catalytic sites. The application of a predetermined concentration of analytes at the peptide interfaces activated the catalytic sites. We observed a relationship between the stability of films and the crystal structure of peptides, and we organized the FF-MNSs into an orthorhombic symmetry that was the most suitable assembly for creation of our biosensors. At 0.1 mol L(-1) NaOH, these FF-MNSs/MCP/Au electrodes have electrocatalytic properties regarding ammonia and urea oxidation that are comparable to those of enzyme-based architectures. Under optimal conditions, the electrocatalytic response is proportional to the ammonia and urea concentration in the range 0.1-1.0 mmol L(-1). The sensitivity was calculated as 2.83 and 81.3 μA mmol L(-1) cm(-2) for ammonia and urea, respectively, at +0.40 V (vs SCE). Our detection method is easy to follow, does not require a mediator or enzyme, and has strong potential for detecting urea via nonenzymatic routes. PMID:25188339

  7. Pulsed EPR for studying silver clusters

    Science.gov (United States)

    Michalik, J.; Wasowicz, T.; Sadlo, J.; Reijerse, E. J.; Kevan, L.

    1996-01-01

    The cationic silver clusters of different nuclearity have been produced by radiolysis of zeolite A and SAPO molecular sieves containing Ag + as exchangeable cations. The pulsed EPR spectroscopy has been applied for studying the local environment of silver cluster in order to understand the mechanism of cluster formation and stabilization. The electron spin echo modulation (ESEM) results on Ag 6n+ cluster in dehydration zeolite A indicate that the hexameric silver is stabilized only in sodalite cages which are surrounded by α-cages containing no water molecules. Trimeric silver clusters formed in hydrated A zeolites strongly interact with water, thus the paramagnetic center can be considered as a cluster-water adduct. In SAPO-molecular sieves, silver clusters are formed only in the presence of adsorbed alcohol molecules. From ESEM it is determined that Ag 4n+ in SAPO-42 is stabilized in α-cages, where it is directly coordinated by two methanol molecules. Dimeric silver, Ag 2+ in SAPO-5 and SAPO-11 is located in 6-ring channels and interacts with three CH 3OH molecules, each in different 10-ring or 12-ring channels. The differences of Ag 2+ stability in SAPO-5 and SAPO-11 are also discussed.

  8. Pulsed EPR for studying silver clusters

    International Nuclear Information System (INIS)

    The cationic silver clusters of different nuclearity have been produced by radiolysis of zeolite A and SAPO molecular sieves containing Ag+ as exchangeable cations. The pulsed EPR spectroscopy has been applied for studying the local environment of silver cluster in order to understand the mechanism of cluster formation and stabilization. the electron spin echo modulation (ESEM) results on Ag6n+ cluster in dehydration zeolite A indicate that the hexameric silver is stabilized only in sodalite cages which are surrounded by α-cages containing no water molecules. Trimeric silver clusters formed in hydrated A zeolites strongly interact with water, thus the paramagnetic center can be considered as a cluster-water adduct. In SAPO-molecular sieves, silver clusters are formed only in the presence of adsorbed alcohol molecules. From ESEM it is determined that Ag4n+ in SAPO-42 is stabilized in α cages, where it is directly coordinated by two methanol molecules. Dimeric silver, Ag2+ in SAPO-5 and SAPO-11 is located in 6-ring channels and interacts with three CH3OH molecules, each in different 10 ring or 12 ring channels. The differences of Ag2+ stability in SAPO-5 and SAPO-11 are also discussed. (Author)

  9. Electrocrystallization and characterization of nanostructured gold and gold alloys

    OpenAIRE

    Yevtushenko, Oleksandra

    2007-01-01

    The kinetics of electrocrystallization of nanostructured gold is investigated and the physical proper-ties of nanostructured materials such as thermal stability, surface roughness and hardness are improved. A new stable non-toxic electrolyte for the electrodeposition of gold and gold alloys is presented. Nanoscaling is achieved by pulse techniques. The possibility of controlling the crystallite size depending on physical and chemical process parameters such as pulse duration, current d...

  10. Cancer Clusters

    Science.gov (United States)

    ... of cancer. Cancer clusters can help scientists identify cancer-causing substances in the environment. For example, in the early 1970s, a cluster ... the area and time period over which the cancers were diagnosed. They also ask about specific environmental hazards or concerns in the affected area. If ...

  11. Synthesis and Characterization of Gold Nanoparticles

    OpenAIRE

    Hedkvist, Olof

    2013-01-01

    This thesis is focused on the synthesis of three different shapes of gold nanoparticles; the gold nanosphere, the gold nanorod and the gold nanocube. These will be synthesized using wet chemistry methods and characterized using UV-Vis- NIR spectroscopy and dynamic light scattering. The results will be used to draw some conclusions as to what factors influence the growth of gold nanoparticles.

  12. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  13. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  14. Clustering processes

    CERN Document Server

    Ryabko, Daniil

    2010-01-01

    The problem of clustering is considered, for the case when each data point is a sample generated by a stationary ergodic process. We propose a very natural asymptotic notion of consistency, and show that simple consistent algorithms exist, under most general non-parametric assumptions. The notion of consistency is as follows: two samples should be put into the same cluster if and only if they were generated by the same distribution. With this notion of consistency, clustering generalizes such classical statistical problems as homogeneity testing and process classification. We show that, for the case of a known number of clusters, consistency can be achieved under the only assumption that the joint distribution of the data is stationary ergodic (no parametric or Markovian assumptions, no assumptions of independence, neither between nor within the samples). If the number of clusters is unknown, consistency can be achieved under appropriate assumptions on the mixing rates of the processes. (again, no parametric ...

  15. Molecular dynamics simulation of gas clusters impact on solid targets

    International Nuclear Information System (INIS)

    The interaction of a cluster of Arn (n=87-300) on a gold and silicon substrate was simulated by use of ordinary and Langevin Molecular Dynamics. The cluster was prepared by cutting out of a spherical f.c.c. block of Dynamics. The Buckingham potential was used for an interaction between the argon atoms. The excitation of the argon atoms due to high temperature and/or high pressure inside the cluster have been taken into account by use of a Monte-Carlo procedure. The N-body potential proposed by Rosato for gold and Axilrod-Teller 3-body potential for silicon was used, which describes well equilibrium properties of bulk material. The substrate was modeled using a b.c.c. lattice (for gold) and diamond (for silicon) of about 30000 atoms. These atoms were separated into three regions, depending on how near they are the impact zone. The atoms of central impact zone are being described by NM. The next zone consists of several semi-spherical layers of a thermal bath, for which the LMD was used. All the other atoms represent the movable (in radial direction) or rigid framework. The kinetic energy of the clusters is varied from 10 to 100 eV/atom. It has been shown that the impact of energetic Ar cluster with the kinetic energy of 100 eV/atom on a gold target sputters not only single atoms but also small gold clusters in the 10 atoms range. Lateral sputtering of gold target material has been predicted. Preliminary results for argon clusters implantation into the silicon (111) shows that this process seems to be quite small due to the very weak bond energy between argon and silicon atoms

  16. Decoupling of epitaxial graphene via gold intercalation probed by dispersive Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Pillai, P. B., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk; DeSouza, M., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk [Semiconductor Materials and Device Group, Electronic and Electrical Engineering, University of Sheffield, Mappin Street, S1 3JD Sheffield (United Kingdom); Narula, R.; Reich, S. [Department of Physics, Freie Universität Berlin, Arnimallee 14, 14195 Berlin (Germany); Wong, L. Y.; Batten, T. [Renishaw, Old Town, Wotton-under-Edge, GL12 7DW Gloucestershire (United Kingdom); Pokorny, J. [Department of Materials Science and Engineering, Sir Robert Hadfield Building, Mappin Street, S1 3JD Sheffield (United Kingdom); Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Praha 8 (Czech Republic)

    2015-05-14

    Signatures of a superlattice structure composed of a quasi periodic arrangement of atomic gold clusters below an epitaxied graphene (EG) layer are examined using dispersive Raman spectroscopy. The gold-graphene system exhibits a laser excitation energy dependant red shift of the 2D mode as compared to pristine epitaxial graphene. The phonon dispersions in both the systems are mapped using the experimentally observed Raman signatures and a third-nearest neighbour tight binding electronic band structure model. Our results reveal that the observed excitation dependent Raman red shift in gold EG primarily arise from the modifications of the phonon dispersion in gold-graphene and shows that the extent of decoupling of graphene from the underlying SiC substrate can be monitored from the dispersive nature of the Raman 2D modes. The intercalated gold atoms restore the phonon band structure of epitaxial graphene towards free standing graphene.

  17. Green Synthesis of Gold Nanoparticles

    OpenAIRE

    Hamid Reza Ghorbani

    2015-01-01

    There is an increased interest in understanding the toxicity and rational design of gold nanoparticles for biomedical applications in recent years. In this study gold nanoparticles were synthesized using dextrose as a reducing agent. The gold nanoparticles displayed characteristic Surface Plasmon Resonance peak at around 550 nm having a mean particle size of 75±30 nm. In order to identify and analyze nanoparticles, UV–Vis spectroscopy, Scanning electron microscopy (SEM), and dynamic light sca...

  18. 31 CFR 100.4 - Gold coin and gold certificates in general.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 1 2010-07-01 2010-07-01 false Gold coin and gold certificates in... EXCHANGE OF PAPER CURRENCY AND COIN In General § 100.4 Gold coin and gold certificates in general. Gold coins, and gold certificates of the type issued before January 30, 1934, are exchangeable, as...

  19. New Trends in Gold Catalysts

    OpenAIRE

    Leonarda F. Liotta

    2014-01-01

    Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growin...

  20. Birth of the localized surface plasmon resonance in monolayer-protected gold nanoclusters.

    Science.gov (United States)

    Malola, Sami; Lehtovaara, Lauri; Enkovaara, Jussi; Häkkinen, Hannu

    2013-11-26

    Gold nanoclusters protected by a thiolate monolayer (MPC) are widely studied for their potential applications in site-specific bioconjugate labeling, sensing, drug delivery, and molecular electronics. Several MPCs with 1-2 nm metal cores are currently known to have a well-defined molecular structure, and they serve as an important link between molecularly dispersed gold and colloidal gold to understand the size-dependent electronic and optical properties. Here, we show by using an ab initio method together with atomistic models for experimentally observed thiolate-stabilized gold clusters how collective electronic excitations change when the gold core of the MPC grows from 1.5 to 2.0 nm. A strong localized surface plasmon resonance (LSPR) develops at 540 nm (2.3 eV) in a cluster with a 2.0 nm metal core. The protecting molecular layer enhances the LSPR, while in a smaller cluster with 1.5 nm gold core, the plasmon-like resonance at 540 nm is confined in the metal core by the molecular layer. Our results demonstrate a threshold size for the emergence of LSPR in these systems and help to develop understanding of the effect of the molecular overlayer on plasmonic properties of MPCs enabling engineering of their properties for plasmonic applications. PMID:24107127

  1. Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yudie [School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026 (China); Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Liu, Honglin, E-mail: hlliu@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Yang, Liangbao, E-mail: lbyang@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Sun, Bai; Liu, Jinhuai [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China)

    2014-05-01

    Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties.

  2. First-principles study of interaction between molecules and gold surface

    International Nuclear Information System (INIS)

    By using density functional theory, the authors have investigated the interaction between a thiol-phenyl molecule (4-4'-dimercapto-biphenyl) and a gold surface. The frontier orbit theory and the perturbation theory are also employed to determine quantitatively the constant of interaction energy. The results show that the bonding between the sulfur atom and the gold atoms corresponds mainly to the covalent bond and some molecular orbits are extended over the molecule and gold cluster which certainly give channels for the charge transport. While the other molecular orbits are localized, charge transport can take place by tunnel mechanism

  3. Real-Time Observation of Reactive Spreading of Gold on Silicon

    OpenAIRE

    Ferralis, Nicola; Gabaly, Farid El; Schmid, Andreas K.; Maboudian, Roya; Carraro, Carlo

    2009-01-01

    The spreading of a bilayer gold film propagating outward from gold clusters, which are pinned to clean Si(111), is imaged in real time by low energy electron microscopy. By monitoring the evolution of the boundary of the gold film at fixed temperature, a linear dependence of the spreading radius on time is found. The measured spreading velocities in the temperature range of 800 < T < 930 K varied from below 100 pm/s to 50 nm/s. We show that the spreading rate is limited by the reaction to for...

  4. Modeling the crystallization of gold nanoclusters-the effect of the potential energy function

    International Nuclear Information System (INIS)

    The crystallization dynamics of 5083 atom gold nanoclusters, which were quenched from the melt, were studied by molecular dynamics (MD) using the EAM 'Glue' and 'Force-matched' potentials to compare and contrast how the crystallization dynamics is affected by these potential energy functions. MD simulations from each potential showed the formation of gold nanoclusters of icosahedral morphology during the quenching process, which is in good agreement with the experimental studies of gold nanoclusters formed under vacuum. The effect of the potential on the evolution of cluster (surface and interior) morphology during the crystallization process is discussed.

  5. Bleaching of sol-gel glass film with embedded gold nanoparticles by thermal poling

    OpenAIRE

    Mezzapesa, Francesco P.; Carvalho, Isabel C. S.; Kazansky, Peter G.; Kawazu, Mitsuhiro; SAKAGUCHI, Koichi

    2006-01-01

    Gold clusters embedded in glass are expected to be hard to dissolve in the form of ions since gold is essentially a nonreactive metal. In spite of that, bleaching of Au-doped nanocomposite sol-gel glass film on a soda-lime glass substrate is demonstrated in which electric-field thermal poling is employed to effectively dissolve randomly distributed gold nanoparticles (15 nm in diameter) embedded in a low conductivity sol-gel glass film with a volume filling factor as small as 2.3%. The surfac...

  6. Use of near-infrared luminescent gold nanoclusters for detection of macrophages

    Science.gov (United States)

    Sapozhnikova, Veronika; Willsey, Brian; Asmis, Reto; Wang, Tianyi; Jenkins, James Travis; Mancuso, Jacob; Ma, Li Leo; Kuranov, Roman; Milner, Thomas E.; Johnston, Keith; Feldman, Marc D.

    2012-02-01

    We determined the effect of aggregation and coating thickness of gold on the luminescence of nanoparticles engulfed by macrophages and in gelatin phantoms. Thin gold-coated iron oxide nanoclusters (nanoroses) have been developed to target macrophages to provide contrast enhancement for near-infrared optical imaging applications. We compare the brightness of nanoroses luminescent emissions in response to 635 nm laser excitation to other nanoparticles including nanoshells, nanorods, and Cy5 conjugated iron oxide nanoparticles. Luminescent properties of all these nanoparticles were investigated in monomeric and aggregated form in gelatin phantoms and primary macrophage cell cultures using confocal microscopy. Aggregation of the gold nanoparticles increased luminescence emission and correlated with increased surface mass of gold per nanoparticle (nanoshells 37+/-14.30×10-3 brightness with 1.23×10-4 wt of gold (g)/nanoparticle versus original nanorose 1.45+/-0.37×10-3 with 2.10×10-16 wt of gold/nanoparticle, p<0.05). Nanoshells showed greater luminescent intensity than original nanoroses or Cy5 conjugated iron oxide nanoparticles when compared as nanoparticles per macrophage (38+/-10 versus 11+/-2.8 versus 17+/-6.5, p<0.05, respectively, ANOVA), but showed relatively poor macrophage uptake (1025+/-128 versus 7549+/-236 versus 96,000 nanoparticles/cell, p<0.05, student t-test nanoshells versus nanoroses). Enhancement of gold fluorescent emissions by nanoparticles can be achieved by reducing the thickness of the gold coating, by clustering the gold on the surface of the nanoparticles (nanoshells), and by clustering the gold nanoparticles themselves.

  7. Clustering analysis

    International Nuclear Information System (INIS)

    Cluster analysis is the name of group of multivariate techniques whose principal purpose is to distinguish similar entities from the characteristics they process.To study this analysis, there are several algorithms that can be used. Therefore, this topic focuses to discuss the algorithms, such as, similarity measures, and hierarchical clustering which includes single linkage, complete linkage and average linkage method. also, non-hierarchical clustering method, which is popular name K-mean method' will be discussed. Finally, this paper will be described the advantages and disadvantages of every methods

  8. Cluster editing

    DEFF Research Database (Denmark)

    Böcker, S.; Baumbach, Jan

    2013-01-01

    The Cluster Editing problem asks to transform a graph into a disjoint union of cliques using a minimum number of edge modifications. Although the problem has been proven NP-complete several times, it has nevertheless attracted much research both from the theoretical and the applied side. The...... algorithms for biological problems. © 2013 Springer-Verlag....... problem has been the inspiration for numerous algorithms in bioinformatics, aiming at clustering entities such as genes, proteins, phenotypes, or patients. In this paper, we review exact and heuristic methods that have been proposed for the Cluster Editing problem, and also applications of these...

  9. Cluster analysis

    CERN Document Server

    Everitt, Brian S; Leese, Morven; Stahl, Daniel

    2011-01-01

    Cluster analysis comprises a range of methods for classifying multivariate data into subgroups. By organizing multivariate data into such subgroups, clustering can help reveal the characteristics of any structure or patterns present. These techniques have proven useful in a wide range of areas such as medicine, psychology, market research and bioinformatics.This fifth edition of the highly successful Cluster Analysis includes coverage of the latest developments in the field and a new chapter dealing with finite mixture models for structured data.Real life examples are used throughout to demons

  10. Cationic Bolaamphiphiles for Gene Delivery

    Science.gov (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  11. Spitzer Clusters

    Science.gov (United States)

    Krick, Kessica

    This proposal is a specific response to the strategic goal of NASA's research program to "discover how the universe works and explore how the universe evolved into its present form." Towards this goal, we propose to mine the Spitzer archive for all observations of galaxy groups and clusters for the purpose of studying galaxy evolution in clusters, contamination rates for Sunyaev Zeldovich cluster surveys, and to provide a database of Spitzer observed clusters to the broader community. Funding from this proposal will go towards two years of support for a Postdoc to do this work. After searching the Spitzer Heritage Archive, we have found 194 unique galaxy groups and clusters that have data from both the Infrared array camera (IRAC; Fazio et al. 2004) at 3.6 - 8 microns and the multiband imaging photometer for Spitzer (MIPS; Rieke et al. 2004) at 24microns. This large sample will add value beyond the individual datasets because it will be a larger sample of IR clusters than ever before and will have sufficient diversity in mass, redshift, and dynamical state to allow us to differentiate amongst the effects of these cluster properties. An infrared sample is important because it is unaffected by dust extinction while at the same time is an excellent measure of both stellar mass (IRAC wavelengths) and star formation rate (MIPS wavelengths). Additionally, IRAC can be used to differentiate star forming galaxies (SFG) from active galactic nuclei (AGN), due to their different spectral shapes in this wavelength regime. Specifically, we intend to identify SFG and AGN in galaxy groups and clusters. Groups and clusters differ from the field because the galaxy densities are higher, there is a large potential well due mainly to the mass of the dark matter, and there is hot X-ray gas (the intracluster medium; ICM). We will examine the impact of these differences in environment on galaxy formation by comparing cluster properties of AGN and SFG to those in the field. Also, we will

  12. Gold phosphide complexes

    OpenAIRE

    2007-01-01

    The vast majority of gold complexes with five group-element donor ligands contain tertiary phosphines, although compounds with amine, arsine or stibine ligands are also known. Although phosphide ligands, which are formed by deprotonation of non-tertiary phosphines, are closely related to the former, they have been employed to a lesser extent, mainly due to their lower stability. Thus, the chemistry of phosphido-bridged derivatives of the main group elements1-3 or transition metals4-6 has been...

  13. Determining gold content

    International Nuclear Information System (INIS)

    A method for determining the gold content of a material, comprises irradiating a body of the material with neutrons and determining the intensity of γ-rays having an energy of 279 keV arising from the reaction 179Au(nn') 179Au → 279 keV. The apparatus has means for conveying the materials past an assembly, which has a neutron source, which does not produce neutrons having sufficient energy to excite fast neutron reactions in non-auriferous constituents. (author)

  14. Paper or Gold

    OpenAIRE

    Mukund Raj

    2003-01-01

    In our society today, money's value is measured by what it can buy—its purchasing power—not by its material worth, but it hasn't always been so. · My previous papers Impact of agriculture output on exchange rates and Currency competition-Survival of the fittest dealt with issues surrounding exchange rate and currency competitions. This paper- Paper or Gold discusses the validity of human society giving importance to paper money. · We all know that the human race always believes in experimenti...

  15. Spontaneous formation of biocompatible vesicles in aqueous mixtures of amino acid-based cationic surfactants and SDS/SDBS.

    Science.gov (United States)

    Shome, Anshupriya; Kar, Tanmoy; Das, Prasanta K

    2011-02-01

    The spontaneous formation of vesicles by six amino acid-based cationic surfactants and two anionic surfactants (sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS)) is reported. The head-group structure of the cationic surfactants is minutely altered to understand their effect on vesicle formation. To establish the regulatory role of the aromatic group in self-aggregation, both aliphatic and aromatic side-chain-substituted amino acid-based cationic surfactants are used. The presence of aromaticity in any one of the constituents favors the formation of vesicles by cationic/anionic surfactant mixtures. The formation of vesicles is primarily dependent on the balance between the hydrophobicity and hydrophilicity of both cationic and anionic surfactants. Vesicle formation is characterized by surface tension, fluorescence anisotropy, transmission electron microscopy, dynamic light scattering, and phase diagrams. These vesicles are thermally stable up to 65 °C, determined by temperature-dependent fluorescence anisotropy. According to the MTT assay, these catanionic vesicles are nontoxic to NIH3T3 cells, thus indicating their wider applicability as delivery vehicles to cells. Among the six cationic surfactants examined, tryptophan- and tyrosine-based surfactants have the ability to reduce HAuCl(4) to gold nanoparticles (GNPs), which is utilized to obtain in-situ-synthesized GNPs entrapped in vesicles without the need for any external reducing agent. PMID:21275029

  16. Identification of the Atomic Scale Structures of the Gold-Thiol Interfaces of Molecular Nanowires by Inelastic Tunneling Spectroscopy

    CERN Document Server

    Demir, Firuz

    2012-01-01

    We examine theoretically the effects of the bonding geometries at the gold-thiol interfaces on the inelastic tunneling spectra of propanedithiolate (PDT) molecules bridging gold electrodes and show that inelastic tunneling spectroscopy combined with theory can be used to determine these bonding geometries experimentally. With the help of density functional theory, we calculate the relaxed geometries and vibrational modes of extended molecules each consisting of one or two PDT molecules connecting two gold nanoclusters. We formulate a perturbative theory of inelastic tunneling through molecules bridging metal contacts in terms of elastic transmission amplitudes, and use this theory to calculate the inelastic tunneling spectra of the gold-PDT-gold extended molecules. We consider PDT molecules with both trans and gauche conformations bound to the gold clusters at top, bridge and hollow bonding sites. Comparing our results with the experimental data of Hihath et al. [Nano Lett. 8, 1673 (2008)], we identify the mo...

  17. The relationship of Au55(PPh3)12Cl6 to colloidal gold

    International Nuclear Information System (INIS)

    The electronic (UV-visible) spectrum of the molecular cluster Au55(PPh3)12Cl6 shows features corresponding to the 520 nm plasma resonance and the shorter-wavelength interband transition of colloidal gold. These absorptions differ qualitatively from the simpler one-electron transitions of lower-nuclearity cluster molecules. Differential scanning calorimetry has been used to measure the enthalpy of decomposition of Au55(PPh3)12Cl6. The Au-Au bonding appears to be substantially stronger than in bulk gold. (orig.)

  18. Cluster Bulleticity

    OpenAIRE

    Massey, Richard; Kitching, Thomas D.; Nagai, Daisuke

    2010-01-01

    The unique properties of dark matter are revealed during collisions between clusters of galaxies, like the bullet cluster (1E 0657-56) and baby bullet (MACSJ0025-12). These systems provide evidence for an additional, invisible mass in the separation between the distribution of their total mass, measured via gravitational lensing, and their ordinary 'baryonic' matter, measured via its X-ray emission. Unfortunately, the information available from these systems is limited by th...

  19. Cluster Bulleticity

    OpenAIRE

    Massey, R; Kitching, T.; Nagai, D.

    2010-01-01

    The unique properties of dark matter are revealed during collisions between clusters of galaxies, such as the bullet cluster (1E 0657−56) and baby bullet (MACS J0025−12). These systems provide evidence for an additional, invisible mass in the separation between the distributions of their total mass, measured via gravitational lensing, and their ordinary ‘baryonic’ matter, measured via its X-ray emission. Unfortunately, the information available from these systems is limited by their rarity. C...

  20. Cluster generator

    Science.gov (United States)

    Donchev, Todor I.; Petrov, Ivan G.

    2011-05-31

    Described herein is an apparatus and a method for producing atom clusters based on a gas discharge within a hollow cathode. The hollow cathode includes one or more walls. The one or more walls define a sputtering chamber within the hollow cathode and include a material to be sputtered. A hollow anode is positioned at an end of the sputtering chamber, and atom clusters are formed when a gas discharge is generated between the hollow anode and the hollow cathode.

  1. Cationic ruthenium alkylidene catalysts bearing phosphine ligands

    OpenAIRE

    Endo, Koji; Grubbs, Robert H.

    2016-01-01

    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bear-ing bulky phosphine ligands. Simple ligand exchange using silver(I) salts of non-coordinating or weakly coordinating anions pro-vided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported...

  2. Cation substitution in two coccolithophore species

    OpenAIRE

    Melteig, Hanna Elina

    2016-01-01

    Few things would be better than getting rid of CO2 while producing useful materials. Coccolithophores use CO2 in their photorespiration, in addition to using CO2 to produce coccoliths – small platelets made of calcite. Ca is a central cation in this process, and the goal of this project is to investigate to what extent other divalent cations can partially substitute for Ca and become part of the growing coccolith. The long term goal is to enable algae to harvest cations and produce mate...

  3. Gold-induced lung disease.

    OpenAIRE

    Heyd, J.; Simmeran, A.

    1983-01-01

    A 70-year-old female with seronegative rheumatoid arthritis developed interstitial pneumonitis while on chrysotherapy. The reversibility of lung disease and favourable response to steroid treatment support the diagnosis of gold-induced lung disease and distinguish this entity from other forms of interstitial lung disease associated with rheumatoid arthritis. The relevant literature related to gold-induced lung disease is briefly reviewed.

  4. Slider Thickness Promotes Lubricity: from 2D Islands to 3D Clusters

    OpenAIRE

    Guerra, Roberto; Tosatti, Erio; Vanossi, Andrea

    2016-01-01

    The sliding of three-dimensional clusters and two-dimensional islands adsorbed on crystal surfaces represent an important test case to understand friction. Even for the same material, monoatomic islands and thick clusters will not as a rule exhibit the same friction, but specific differences have not been explored. Through realistic molecular dynamics simulations of the static friction gold on graphite, an experimentally relevant system, we uncover as a function of gold thickness a progressiv...

  5. The adjuvanticity of gold nanoparticles

    Science.gov (United States)

    Dykman, Lev A.; Bogatyrev, Vladimir A.; Staroverov, Sergey A.; Pristensky, Dmitry V.; Shchyogolev, Sergey Yu.; Khlebtsov, Nikolai G.

    2006-06-01

    A new variant of a technique for in vivo production of antibodies to various antigens with colloidal-gold nanoparticles as carrier is discussed. With this technique we obtained highly specific and relatively high-titre antibodies to different antigens. The antibodies were tested by an immunodot assay with gold nanoparticle markers. Our results provide the first demonstration that immunization of animals with colloidal gold complexed with either haptens or complete antigens gives rise to highly specific antibodies even without the use of complete Freund's adjuvant. These findings may attest to the adjuvanticity of gold nanoparticles itself. We provide also experimental results and discussion aimed at elucidation of possible mechanisms of the discovered colloidal-gold-adjuvanticity effect.

  6. Colloidal stability of gold nanorod solution upon exposure to excised human skin: Effect of surface chemistry and protein adsorption.

    Science.gov (United States)

    Mahmoud, Nouf N; Al-Qaoud, Khaled M; Al-Bakri, Amal G; Alkilany, Alaaldin M; Khalil, Enam A

    2016-06-01

    In this study, we evaluated the colloidal stability of gold nanorods (with positive, negative and neutral surface charge) in solution upon contact with excised human skin. UV-vis absorption, plasmon peak broadening index (PPBI%) and transmission electron microscope analysis were used to follow nanoparticles aggregation in solution. Our results show that positively charged gold nanorods aggregate extensively upon exposure to excised human skin compared to negatively and neutrally charged gold nanorods. Skin-induced aggregation of cationic gold nanorods was linked to the adsorption of proteins released from the dermis layer to the surface of gold nanorods. Protein adsorption significantly screen nanorod's effective surface charge and induce their aggregation. Moreover, we demonstrate that the presence of polyethylene glycol polymer on the surface of cationic gold nanorods minimize this aggregation significantly by providing steric repulsion (non-electrostatic stabilization mechanism). This work highlights the importance of evaluating the colloidal stability of nanoparticles in solution upon contact with skin, which is a "usually overlooked" parameter when studying the nanoparticle-skin interaction. PMID:26923289

  7. 'Methane oxidation on supported gold catalysts'

    DEFF Research Database (Denmark)

    Walther, Guido

    2008-01-01

    Methane (CH4), a major compound of natural gas, has been suggested as a future energy carrier. However, it is also known to be a strong greenhouse gas. The use of CH4 obtained from crude oil as an associated gas is often uneconomical, and it is thus burned off. Avoiding flaring and making the...... steady-state activity measurements were performed to obtain the reaction rates for CO and H2 oxidation. These reactions were studied on three different gold particle sizes using either O2 or N2O as oxidation agents. Using particle size distributions obtained from TEM analysis, it was found that the CO...... oxidation rates follow the d−3 relationship proposed in [Nano Today 2, 14 (2007)]. To corroborate the experimental findings, density functional theory (DFT) calculations on the Auf532g surface and a Au12 cluster, which model corner sites, were used in a microkinetic model. This model reproduced the apparent...

  8. Coalescence and Collisions of Gold Nanoparticles

    Directory of Open Access Journals (Sweden)

    Eduardo Pérez-Tijerina

    2011-01-01

    Full Text Available We study the assembling of small gold clusters subject to collisions and close contact coalescence by using molecular dynamics simulations to simulate events that occur typically in the sputtering process of synthesis. Our results support the notion that the kinetics of coalescence processes strongly determine the geometry and structure of the final particle. While impact velocities, relative orientations, and the initial shape of the interacting particles are unlikely to strictly determine the structural details of the newly formed particle, we found that high initial temperatures and/or impact velocities increase the probability of appearance of icosahedral-like structures, Wulff polyhedra are likely to be formed as a product of the interactions between nanospheres, while the appearance of fcc particles of approximately cuboctahedral shape is mainly due to the interaction between icosahedra.

  9. Differentiation of cancer cell type and phenotype using quantum dot-gold nanoparticle sensor arrays

    OpenAIRE

    Liu, Qian; Yeh, Yi-Cheun; Rana, Subinoy; Jiang, Ying; Guo, Lin; Rotello, Vincent M.

    2012-01-01

    We demonstrate rapid and efficient sensing of mammalian cell types and states using nanoparticle-based sensor arrays. These arrays are comprised of cationic quantum dots (QDs) and gold nanoparticles (AuNPs) that interact with cell surfaces to generate distinguishable fluorescence responses based on cell surface signatures. The use of QDs as the recognition elements as well as the signal transducers presents the potential for direct visualization of selective cell surface interactions. Notably...

  10. Magnetron sputtering cluster apparatus for formation and deposition of size-selected metal nanoparticles

    OpenAIRE

    Hanif, Muhammad; Popok, Vladimir

    2015-01-01

    The experimental setup utilizing a DC magnetron sputtering source for production of metal clusters, their size (mass) selection and following deposition in high vacuum is described. The source is capable to form clusters of various metals, for example, copper, silver, gold etc. Cluster size selection is achieved using an electrostatic quadrupole mass selector. The deposited silver clusters are studied using atomic force microscopy. The height distributions show typical relative standard size ...

  11. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.

    2015-01-01

    Roč. 115, 22 January (2015), s. 551-558. ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.074, year: 2014

  12. Organic non-aqueous cation-based redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

    2016-03-29

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  13. Structures of Aln, its anions and cations up to n=34: A theoretical investigation

    International Nuclear Information System (INIS)

    A systematic density functional study has been performed for neutral and singly charged clusters of aluminum with up to 34 atoms. A thorough search for global minimum structures has been carried out for Aln employing genetic algorithm and basin-hopping procedures. For Aln this confirms results of previous investigations up to n=22; new global minima have been located for n=23-31, 33. Structures for singly charged cations and anions have been obtained by reoptimization of the pool of 40 low-energy structures of the neutral clusters. The global minima of charged and neutral clusters are always low-spin states with the possible exception of a triplet state of Al28, which is isoenergetic with a singlet. The cluster structures are mostly quite irregular and do not resemble fractions of the fcc bulk phase. High symmetries are found only for the global minimum of Al23 and the triplet state of Al28.

  14. Cation locations and dislocations in zeolites

    Science.gov (United States)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  15. Scanning tunneling microscopy studies of glucose oxidase on gold surface

    International Nuclear Information System (INIS)

    Full text: Three immobilization methods have been used for scanning tunneling microscopy (STM) studies of glucose oxidase (GOD) on gold. They are based on a) physical adsorption from solution, b) microcontact printing and c) covalent bonding onto self-assembled monolayers (SAM) of 3-mercaptopropionic acid (MPA). The STM images are used to provide information about the organization of individual GOD molecules and more densely packed monolayers of GOD on electrode surfaces, thus providing information of the role of interfacial structure on biosensor performance. The use of atomically flat gold substrates enables easy distinction of deposited enzyme features from the flat gold substrate. Microcontact printing is found to be a more reliable method than adsorption from solution for preparing individual GOD molecules on the gold surface STM images of printed samples reveal two different shapes of native GOD molecules. One is a butterfly shape with dimensions of 10 ± 1 nm x 6 ± 1 nm, assigned to the lying position of molecule while the second is an approximately spherical shape with dimensions of 6.5 ± 1 nm x 5 ± 1nm assigned to a standing position. Isolated clusters of 5 to 6 GOD molecules are also observed. With monolayer coverage, GOD molecules exhibit a tendency to organize themselves into a two dimensional array with adequate sample stability to obtain high-resolution STM images. Within these two-dimensional arrays are clearly seen repeating clusters of five to six enzyme molecules in a unit STM imaging of GOD monolayers covalently immobilized onto SAM (MPA) are considerably more difficult than when the enzyme is adsorbed directly onto the metal. Cluster structures are observed both high and low coverage despite the fact that native GOD is a negatively charged molecule. Copyright (2002) Australian Society for Electron Microscopy Inc

  16. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  17. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

  18. Silica-based cationic bilayers as immunoadjuvants

    OpenAIRE

    Carmona-Ribeiro Ana M; da Costa Maria; Faquim-Mauro Eliana; Santana Mariana RA; Lincopan Nilton

    2009-01-01

    Abstract Background Silica particles cationized by dioctadecyldimethylammonium bromide (DODAB) bilayer were previously described. This work shows the efficiency of these particulates for antigen adsorption and presentation to the immune system and proves the concept that silica-based cationic bilayers exhibit better performance than alum regarding colloid stability and cellular immune responses for vaccine design. Results Firstly, the silica/DODAB assembly was characterized at 1 mM NaCl, pH 6...

  19. Cations and activated sludge floc structure

    OpenAIRE

    Park, Chul

    2002-01-01

    This research was designed to investigate the effect of cations on activated sludge characteristics and also to determine their influence on digestion performance. For this purpose, cations in solution and in floc were evaluated along with various activated sludge characteristics and the collected waste activated sludge underwent both anaerobic and aerobic digestion. It was found that large amounts of biopolymer (protein + polysaccharide) remained in the effluent of WWTP that received high in...

  20. Cationic Closo-carboranes 2. Do computed 11B and 13C NMR chemical shifts support their experimental availability?

    Czech Academy of Sciences Publication Activity Database

    Hnyk, Drahomír; Jayasree, E.G.

    2013-01-01

    Roč. 34, č. 8 (2013), s. 656-661. ISSN 0192-8651 R&D Projects: GA ČR GAP208/10/2269 Institutional support: RVO:61388980 Keywords : boron clusters * weakly-coordinating cations * 11B NMR * dynamic electron correlation Subject RIV: CA - Inorganic Chemistry Impact factor: 3.601, year: 2013

  1. Intrinsic multistate switching of gold clusters through electrochemical gating

    DEFF Research Database (Denmark)

    Albrecht, Tim; Mertens, S.F.L.; Ulstrup, Jens

    2007-01-01

    The electrochemical behavior of small metal nanoparticles is governed by Coulomb-like charging and equally spaced charge-transfer transitions. Using electrochemical gating at constant bias voltage, we show, for the first time, that individual nanoparticles can be operated as multistate switches in...

  2. Denominators of cluster variables

    OpenAIRE

    Buan, Aslak Bakke; Marsh, Robert J.; Reiten, Idun

    2007-01-01

    Associated to any acyclic cluster algebra is a corresponding triangulated category known as the cluster category. It is known that there is a one-to-one correspondence between cluster variables in the cluster algebra and exceptional indecomposable objects in the cluster category inducing a correspondence between clusters and cluster-tilting objects. Fix a cluster-tilting object T and a corresponding initial cluster. By the Laurent phenomenon, every cluster variable can be written as a Laurent...

  3. Dynamics of Ag clusters on complex surfaces: Molecular dynamics simulations

    Science.gov (United States)

    Alkis, S.; Krause, J. L.; Fry, J. N.; Cheng, H.-P.

    2009-03-01

    We study the diffusion of silver nanoparticles on self-assembled monolayers (SAMs). Silver clusters Agn of sizes n=55 , 147, and 1289 were evolved in contact with an alkanethiol (12 carbon, dodecanethiol) SAM deposited on a gold (111) surface. Analysis based on classical molecular dynamics simulations reveals that these systems exhibit a rich variety of behaviors, from superdiffusive for the lightest cluster to pinned for the heaviest, evolution self-similar in lengths and times for the lightest cluster but with characteristic time scales and directional anisotropies emerging for the heavier clusters.

  4. Understanding the catalytic activity of gold nanoparticles through multi-scale simulations

    DEFF Research Database (Denmark)

    Brodersen, Simon Hedegaard; Vej-Hansen, Ulrik Grønbjerg; Larsen, Britt Hvolbæk;

    2011-01-01

    We investigate how the chemical reactivity of gold nanoparticles depends on the cluster size and shape using a combination of simulation techniques at different length scales, enabling us to model at the atomic level the shapes of clusters in the size range relevant for catalysis. The detailed...... atomic configuration of a nanoparticle with a given number of atoms is calculated by first finding overall cluster shapes with low energy and approximately the right size, and then using Metropolis Monte Carlo simulations to identify the detailed atomic configuration. The equilibrium number of low...... in excellent agreement with experiments, and we conclude that the experimentally observed trends are mostly explained by the high reactivity of under-coordinated corner atoms on the gold clusters. Other effects, such as the effect of the substrate, may influence the reactivities significantly, but...

  5. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation

    Science.gov (United States)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

    2016-05-01

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  6. Stealing the Gold

    International Nuclear Information System (INIS)

    Stealing the Gold presents a survey of some of the most exciting topics in condensed matter physics today, from the perspective of the pioneering work of Sam Edwards. Original articles from leaders in the field, including several Nobel laureates, highlight the historical development as well as new and emerging areas. This book would be of interest to graduate students and researchers in condensed matter physics, statistical physics and theoretical physics. Over the course of nearly half a century, Sam Edwards has led the field of condensed matter physics in new directions, ranging from the electronic and statistical properties of disordered materials to the mechanical properties of granular materials. Along the way he has provided seminal contributions to fluid mechanics, polymer science, surface science and statistical mechanics. This volume celebrates the immense scope of his influence by presenting a collection of original articles by recognized leaders in theoretical physics, including two Nobel laureates and a Fields medalist, which describe the genesis, evolution and future prospects of the various sub-fields of condensed matter theory, along with reprints of a selection of Edwards' seminal papers that helped give birth to the subject. Stealing the Gold, Edwards' favourite caricature of the relationship between theoretical physicists and nature, will be of singular interest to graduate students looking for an overview of some of the most exciting areas of theoretical physics, as well as to researchers in condensed matter physics looking for a comprehensive, broad and uniquely incisive snapshot of their subject at the dawn of the 21st century. (book review)

  7. Cluster Bulleticity

    CERN Document Server

    Massey, Richard; Nagai, Daisuke

    2010-01-01

    The unique properties of dark matter are revealed during collisions between clusters of galaxies, like the bullet cluster (1E 0657-56) and baby bullet (MACSJ0025-12). These systems provide evidence for an additional, invisible mass in the separation between the distribution of their total mass, measured via gravitational lensing, and their ordinary 'baryonic' matter, measured via its X-ray emission. Unfortunately, the information available from these systems is limited by their rarity. Constraints on the properties of dark matter, such as its interaction cross-section, are therefore restricted by uncertainties in the individual systems' impact velocity, impact parameter and orientation with respect to the line of sight. Here we develop a complementary, statistical measurement in which every piece of substructure falling into every massive cluster is treated as a bullet. We define 'bulleticity' as the mean separation between dark matter and ordinary matter, and we measure a positive signal in hydrodynamical si...

  8. Synthesis of gold structures by gold-binding peptide governed by concentration of gold ion and peptide.

    Science.gov (United States)

    Kim, Jungok; Kim, Dong-Hun; Lee, Sylvia J; Rheem, Youngwoo; Myung, Nosang V; Hur, Hor-Gil

    2016-08-01

    Although biological synthesis methods for the production of gold structures by microorganisms, plant extracts, proteins, and peptide have recently been introduced, there have been few reports pertaining to controlling their size and morphology. The gold ion and peptide concentrations affected on the size and uniformity of gold plates by a gold-binding peptide Midas-11. The higher concentration of gold ions produced a larger size of gold structures reached 125.5 μm, but an increased amount of Midas-11 produced a smaller size of gold platelets and increased the yield percentage of polygonal gold particles rather than platelets. The mechanisms governing factors controlling the production of gold structures were primarily related to nucleation and growth. These results indicate that the synthesis of gold architectures can be controlled by newly isolated and substituted peptides under different reaction conditions. PMID:27108675

  9. GOLD and the fixed ratio

    Directory of Open Access Journals (Sweden)

    Vestbo J

    2012-09-01

    Full Text Available Jørgen VestboUniversity of Manchester, Manchester, UKI read with interest the paper entitled "Diagnosis of airway obstruction in the elderly: contribution of the SARA study" by Sorino et al in a recent issue of this journal.1 Being involved in the Global Initiative for Obstructive Lung Diseases (GOLD, it is nice to see the interest sparked by the GOLD strategy document. However, in the paper by Sorino et al, there are a few misunderstandings around GOLD and the fixed ratio (forced expiratory volume in 1 second/forced volume vital capacity < 0.70 that need clarification.View original paper by Sorino and colleagues.

  10. Gold based bulk metallic glass

    OpenAIRE

    Schroers, Jan; Lohwongwatana, Boonrat; Johnson, William L.; Peker, Atakan

    2005-01-01

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5 mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644 K, a glass transition temperature of 401 K, and a supercooled liquid region of 58 K. The Vickers hardness of the alloys in this system...

  11. Directed Assembly of Gold Nanoparticles

    DEFF Research Database (Denmark)

    Westerlund, Axel Rune Fredrik; Bjørnholm, Thomas

    2009-01-01

    As a complement to common "top-down" lithography techniques, "bottom-up" assembly techniques are emerging as promising tools to build nanoscale structures in a predictable way. Gold nanoparticles that are stable and relatively easy to synthesize are important building blocks in many such structures...... due to their useful optical and electronic properties. Programmed assembly of gold nanoparticles in one, two, and three dimensions is therefore of large interest. This review focuses on the progress from the last three years in the field of directed gold nanoparticle and nanorod assembly using...

  12. Ultrasmooth, Highly Spherical Monocrystalline Gold Particles for Precision Plasmonics

    KAUST Repository

    Lee, You-Jin

    2013-12-23

    Ultrasmooth, highly spherical monocrystalline gold particles were prepared by a cyclic process of slow growth followed by slow chemical etching, which selectively removes edges and vertices. The etching process effectively makes the surface tension isotropic, so that spheres are favored under quasi-static conditions. It is scalable up to particle sizes of 200 nm or more. The resulting spherical crystals display uniform scattering spectra and consistent optical coupling at small separations, even showing Fano-like resonances in small clusters. The high monodispersity of the particles we demonstrate should facilitate the self-assembly of nanoparticle clusters with uniform optical resonances, which could in turn be used to fabricate optical metafluids. Narrow size distributions are required to control not only the spectral features but also the morphology and yield of clusters in certain assembly schemes. © 2013 American Chemical Society.

  13. Divergent Gold(I)-Catalyzed Skeletal Rearrangements of 1,7-Enynes.

    Science.gov (United States)

    Meiß, Rebecca; Kumar, Kamal; Waldmann, Herbert

    2015-09-21

    The gold(I) complex catalyzed cycloisomerization and skeletal rearrangement of 1,n-enynes (n=5-7) is a powerful methodology for the efficient synthesis of complex molecular architectures. In contrast to 1,6-enynes, readily accessible homologous 1,7-enynes are largely unexplored in such transformations. Here, the divergent skeletal rearrangement of all-carbon 1,7-enynes by catalysis with a cationic gold(I) complex is reported. Depending on electronic and steric factors, differently substituted 1,7-enynes react via different carbocations formed from a common gold carbene intermediate to yield on the one hand novel exocyclic allenes and on the other hand tricyclic hexahydro-anthracenes through a novel dehydrogenative Diels-Alder reaction. PMID:26356499

  14. Induction of apoptosis in human cancer cells by targeting mitochondria with gold nanoparticles.

    Science.gov (United States)

    Mkandawire, M M; Lakatos, M; Springer, A; Clemens, A; Appelhans, D; Krause-Buchholz, U; Pompe, W; Rödel, G; Mkandawire, M

    2015-06-28

    A major challenge in designing cancer therapies is the induction of cancer cell apoptosis, although activation of intrinsic apoptotic pathways by targeting gold nanoparticles to mitochondria is promising. We report an in vitro procedure targeting mitochondria with conjugated gold nanoparticles and investigating effects on apoptosis induction in the human breast cancer cell line Jimt-1. Gold nanoparticles were conjugated to a variant of turbo green fluorescent protein (mitoTGFP) harbouring an amino-terminal mitochondrial localization signal. Au nanoparticle conjugates were further complexed with cationic maltotriose-modified poly(propylene imine) third generation dendrimers. Fluorescence and transmission electron microscopy revealed that Au nanoparticle conjugates were directed to mitochondria upon transfection, causing partial rupture of the outer mitochondrial membrane, triggering cell death. The ability to target Au nanoparticles into mitochondria of breast cancer cells and induce apoptosis reveals an alternative application of Au nanoparticles in photothermal therapy of cancer. PMID:26022234

  15. 41 CFR 101-45.002 - Gold.

    Science.gov (United States)

    2010-07-01

    ... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Gold. 101-45.002 Section... PERSONAL PROPERTY § 101-45.002 Gold. (a) Gold will be sold in accordance with this section and part 102-38 of the Federal Management Regulation. (b) Sales of gold shall be processed to— (1) Use the sealed...

  16. Chloride sublimation of gold-arsenic concentrates

    International Nuclear Information System (INIS)

    Present article is devoted to chloride sublimation of gold-arsenic concentrates. The results of studies of chloride sublimation of gold-arsenic comprising concentrates of Chore deposit of Tajikistan are considered. It is found that by application sodium chloride for gold-arsenic comprising concentrates it is possible to extract gold and silver from flotation concentrates.

  17. Enhancement of gold recovery using bioleaching from gold concentrate

    Science.gov (United States)

    Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

    2012-04-01

    The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

  18. Protein-mediated autoreduction of gold salts to gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Nivedita; Bhattacharya, Resham; Mukherjee, Priyabrata [Department of Biochemistry and Molecular Biology, College of Medicine, Mayo Clinic, Rochester, MN 55905 (United States)], E-mail: Mukherjee.Priyabrata@mayo.edu

    2008-09-01

    Here we report for the first time that proteins can function as unique reducing agents to produce gold nanoparticles from gold salts. We demonstrate that three different proteins, namely, bovine serum albumin (BSA), Rituximab (RIT-an anti-CD20 antibody) and Cetuximab (C225-anti-EGFR antibody), reduce gold salts to gold nanoparticles (GNP). Interestingly, among all the three proteins tested, only BSA can reduce gold salts to gold nanotriangles (GNT). BSA-induced formation of GNT can be controlled by carefully selecting the reaction condition. Heating or using excess of ascorbic acid (AA) as additional reducing agent shifts the reaction towards the formation of GNP with flower-like morphology, whereas slowing down the reaction either by cooling or by adding small amount of AA directs the synthesis towards GNT formation. GNT is formed only at pH 3; higher pHs (pH 7 and pH 10) did not produce any nanoparticles, suggesting the involvement of specific protein conformation in GNT formation. The nanomaterials formed by this method were characterized using UV-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). This is an important finding that will have uses in various nanotechnological applications, particularly in the green synthesis of novel nanomaterials based on protein structure.

  19. Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

    International Nuclear Information System (INIS)

    This invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerator compounds for labelling such cationic radiodiagnostic agents, kits for preparing such 99mTc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium

  20. Fuzzy Clustering

    DEFF Research Database (Denmark)

    Berks, G.; Keyserlingk, Diedrich Graf von; Jantzen, Jan;

    2000-01-01

    and clustering are the basic concerns in medicine. Classification depends on definitions of the classes and their required degree of participant of the elements in the cases' symptoms. In medicine imprecise conditions are the rule and therefore fuzzy methods are much more suitable than crisp ones...

  1. Dual restriction enzyme digest of cationic-gold-coated DNA scaffolds

    OpenAIRE

    Slavin, John WJ; Ivanisevic, Albena

    2007-01-01

    DNA strands coated with AuNPs were cleaved by restriction enzymes while in solution or on a surface. Enzymatic activity was verified by gel electrophoresis prior to surface analysis. Cleavage results suggest that enzymes can recognize the AuNP-coated strands while on the surfaces, though specificity in digestion has not yet been verified. Development allows for advances in site specific localization of components using biological media.

  2. Quotients of cluster categories

    OpenAIRE

    Jorgensen, Peter

    2007-01-01

    Higher cluster categories were recently introduced as a generalization of cluster categories. This paper shows that in Dynkin types A and D, half of all higher cluster categories are actually just quotients of cluster categories. The other half can be obtained as quotients of 2-cluster categories, the "lowest" type of higher cluster categories. Hence, in Dynkin types A and D, all higher cluster phenomena are implicit in cluster categories and 2-cluster categories. In contrast, the same is not...

  3. Gold, currencies and market efficiency

    Science.gov (United States)

    Kristoufek, Ladislav; Vosvrda, Miloslav

    2016-05-01

    Gold and currency markets form a unique pair with specific interactions and dynamics. We focus on the efficiency ranking of gold markets with respect to the currency of purchase. By utilizing the Efficiency Index (EI) based on fractal dimension, approximate entropy and long-term memory on a wide portfolio of 142 gold price series for different currencies, we construct the efficiency ranking based on the extended EI methodology we provide. Rather unexpected results are uncovered as the gold prices in major currencies lay among the least efficient ones whereas very minor currencies are among the most efficient ones. We argue that such counterintuitive results can be partly attributed to a unique period of examination (2011-2014) characteristic by quantitative easing and rather unorthodox monetary policies together with the investigated illegal collusion of major foreign exchange market participants, as well as some other factors discussed in some detail.

  4. Gold based bulk metallic glass

    Science.gov (United States)

    Schroers, Jan; Lohwongwatana, Boonrat; Johnson, William L.; Peker, Atakan

    2005-08-01

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644K, a glass transition temperature of 401K, and a supercooled liquid region of 58K. The Vickers hardness of the alloys in this system is ˜350Hv, twice that of conventional 18-karat crystalline gold alloys. This combination of properties makes the alloys attractive for many applications including electronic, medical, dental, surface coating, and jewelry.

  5. Gold based bulk metallic glass

    International Nuclear Information System (INIS)

    Gold-based bulk metallic glass alloys based on Au-Cu-Si are introduced. The alloys exhibit a gold content comparable to 18-karat gold. They show very low liquidus temperature, large supercooled liquid region, and good processibility. The maximum casting thickness exceeds 5 mm in the best glassformer. Au49Ag5.5Pd2.3Cu26.9Si16.3 has a liquidus temperature of 644 K, a glass transition temperature of 401 K, and a supercooled liquid region of 58 K. The Vickers hardness of the alloys in this system is ∼350 Hv, twice that of conventional 18-karat crystalline gold alloys. This combination of properties makes the alloys attractive for many applications including electronic, medical, dental, surface coating, and jewelry

  6. Discovery of the Gold Isotopes

    OpenAIRE

    Schuh, A.; A. Fritsch; Ginepro, J. Q.; Heim, M.; SHORE, A.; Thoennessen, M

    2009-01-01

    Thirty-six gold isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  7. A eutectic gold vapour laser

    Science.gov (United States)

    Tou, T. Y.; Cheak, K. E.; Low, K. S.

    This paper presents a eutectic gold vapour laser (EGVL) which uses the eutectic alloy of gold and silicon, Au/3.15Si, as the lasant. It was observed that, at low input power operation, the presence of the silicon vapour could increase the output of the 627.8 nm laser line by (50-60)% when compared with a gold vapour laser (GVL) which uses pure gold as the lasant. The improved laser output for the EGVL may be explained by an increased electron density, as a result of Penning ionization of silicon atoms. However, for higher input power operation, the EGVL showed a slower rate of increase in its laser output power and was overtaken by GVLs at a tube operating temperature of around 1650°C. This may be explained by a lowering of the electron temperature owing to increasing inelastic collisions between the electrons and silicon atoms which, although excited, may not produce additional electrons.

  8. Gold nanoparticles for cancer detection and treatment: The role of adhesion

    International Nuclear Information System (INIS)

    This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia

  9. Gold nanoparticles for cancer detection and treatment: The role of adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Oni, Y. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Hao, K. [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Dozie-Nwachukwu, S.; Odusanya, O. S. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Sheda Science and Technology Complex (SHESTCO), Gwagwalada, Abuja, Federal Capital Territory (Nigeria); Obayemi, J.D. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Anuku, N. [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Department of Chemistry and Chemical Technology, Bronx Community College, New York, New York 10453 (United States); Soboyejo, W. O. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria)

    2014-02-28

    This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.

  10. Gold nanoparticles for cancer detection and treatment: The role of adhesion

    Science.gov (United States)

    Oni, Y.; Hao, K.; Dozie-Nwachukwu, S.; Obayemi, J. D.; Odusanya, O. S.; Anuku, N.; Soboyejo, W. O.

    2014-02-01

    This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.

  11. Characterisation of gold from Fiji

    OpenAIRE

    Naden, Jon; Henney, P.J.

    1995-01-01

    This is a study of the variation in chemistry and inclusion mineralogy of bedrock and placer gold from Fiji. It forms part of a large project, undertaking gold characterisation from a wide range of geological environments in Ecuador, Zimbabwe, Malaysia and Fiji. The work was carried out under the Overseas Development AdministratiodBritish Geological Survey Technology Development and Research programme (Project R5549) as part of the British Government’s provision of technical...

  12. Coalescence Behavior of Gold Nanoparticles

    OpenAIRE

    Wang YQ; Liang WS; Geng CY

    2009-01-01

    Abstract The tetraoctylammonium bromide (TOAB)-stabilized gold nanoparticles have been successfully fabricated. After an annealing of the as-synthesized nanoparticles at 300 °C for 30 min, the coalescence behavior of gold nanoparticles has been investigated using high-resolution transmission electron microscopy in detail. Two types of coalescence, one being an ordered combination of two or more particles in appropriate orientations through twinning, and the other being an ordered combina...

  13. Regional Innovation Clusters

    Data.gov (United States)

    Small Business Administration — The Regional Innovation Clusters serve a diverse group of sectors and geographies. Three of the initial pilot clusters, termed Advanced Defense Technology clusters,...

  14. Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jing; Aydin, C.; Browning, Nigel D.; Gates, Bruce C.

    2012-06-11

    Gold, the most stable metallic element, attracted wide attention as a catalyst only after the discovery that gold nanoclusters on oxide supports are highly active and selective for reactions including numerous oxidation,[1–8] hydrogenation,[9–11] hydroamination,[12, 13] ring expansion,[14, 15] and coupling[16, 17] reactions. The catalytic properties of supported gold strongly dependent on the gold–support interactions and the size of the active species, which must be small—typically clusters with diameters of the order of 1 nm.[18–20] Frequent discoveries of new gold-catalyzed reactions are leading the science; understanding has been slow to emerge.[21] Major challenges are to identify the catalytically active species and to characterize gold–support interactions.

  15. Vibrational identification for conformations of trans-1,2-bis (4-pyridyl) ethylene in gold molecular junctions

    Science.gov (United States)

    Hu, Wei; Tian, Guangjun; Duan, Sai; Lin, Li-Li; Ma, Yong; Luo, Yi

    2015-05-01

    The surface-enhanced Raman scattering (SERS) spectroscopy and inelastic electron tunneling spectroscopy (IETS) are employed to study trans-1,2-bis (4-pyridyl) ethylene (BPE)/gold system. Both junction and complex forms are considered for the SERS simulations. It is predicted that the peak at 1581 cm-1 is more intense in the junction forms than that in the complex forms. Time dependent density functional theory calculations show that the relative intensity is mainly controlled by the excitation energy derivative respect to the normal modes, and the total intensity is governed by the excitation energy of the excited states. The Csbnd H bending modes dominate the IET spectra when BPE adsorbed on the flat gold surfaces. While, the pyridyl ring deformation modes are more active when BPE adsorbed on the edge of the gold clusters. For BPE adsorbed on the tip of gold clusters, the pyridyl ring and Cdbnd C stretching modes show significant contribution to the IET spectra.

  16. DNA templates silver clusters with magic sizes and colors for multi-cluster fluorescent assemblies

    Science.gov (United States)

    Copp, Stacy

    2015-03-01

    The natural inclusion of information in DNA, a vital part of life's rich complexity, can also be exploited to create diverse structures with multiple scales of complexity. Now emerging in novel photonic applications, DNA-stabilized silver clusters (AgN-DNA) are compelling examples of multi-scale DNA-directed assembly: individual fluorescent clusters, each templated by specific DNA base motifs, can then be arranged together in DNA-mediated multi-cluster assemblies with nanoscale precision. We discuss how DNA imbues AgN-DNA with unique features. Our optical data on pure AgN-DNA show that DNA base-cationic silver ligands impose rod-like shapes for neutral silver clusters, whose length primarily determines fluorescence color. This shape anisotropy leads to the aspherical AgN-DNA magic number cluster sizes and ``magic color'' groupings. We exploit DNA's sequence properties to extract multi-base motifs that select certain magic cluster sizes, using machine learning algorithms applied to large data sets. With these base motifs, we design DNA scaffolds to arrange multiple atomically precise AgN together in nanoscale proximity. We demonstrate that clusters are stable when held at separations below 10 nm, both in bicolor, dual cluster DNA clamp assemblies and in one-dimensional assemblies of atomically precise clusters arrayed on DNA nanotubes. Supported by NSF-CHE-1213895 and NSF-DMR-1309410. SMC acknowledges NSF-DGE-1144085, a NSF GRFP.

  17. Single pass kernel -means clustering method

    Indian Academy of Sciences (India)

    T Hitendra Sarma; P Viswanath; B Eswara Reddy

    2013-06-01

    In unsupervised classification, kernel -means clustering method has been shown to perform better than conventional -means clustering method in identifying non-isotropic clusters in a data set. The space and time requirements of this method are $O(n^2)$, where is the data set size. Because of this quadratic time complexity, the kernel -means method is not applicable to work with large data sets. The paper proposes a simple and faster version of the kernel -means clustering method, called single pass kernel k-means clustering method. The proposed method works as follows. First, a random sample $\\mathcal{S}$ is selected from the data set $\\mathcal{D}$. A partition $\\Pi_{\\mathcal{S}}$ is obtained by applying the conventional kernel -means method on the random sample $\\mathcal{S}$. The novelty of the paper is, for each cluster in $\\Pi_{\\mathcal{S}}$, the exact cluster center in the input space is obtained using the gradient descent approach. Finally, each unsampled pattern is assigned to its closest exact cluster center to get a partition of the entire data set. The proposed method needs to scan the data set only once and it is much faster than the conventional kernel -means method. The time complexity of this method is $O(s^2+t+nk)$ where is the size of the random sample $\\mathcal{S}$, is the number of clusters required, and is the time taken by the gradient descent method (to find exact cluster centers). The space complexity of the method is $O(s^2)$. The proposed method can be easily implemented and is suitable for large data sets, like those in data mining applications. Experimental results show that, with a small loss of quality, the proposed method can significantly reduce the time taken than the conventional kernel -means clustering method. The proposed method is also compared with other recent similar methods.

  18. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.

    1991-10-01

    The objective of this project is to make use of products obtained from renewable plant sources as monomers for the direct production of polymers which can be used for a wide range of plastic applications. In this report is described progress in the synthesis and polymerization of cationically polymerizable monomers and oligomers derived from botanical oils, terpenes, natural rubber, and lignin. Nine different botanical oils were obtained from various sources, characterized and then epoxidized. Their photopolymerization was carried out using cationic photoinitiators and the mechanical properties of the resulting polymers characterized. Preliminary biodegradation studies are being conducted on the photopolymerized films from several of these oils. Limonene was cationically polymerized to give dimers and the dimers epoxidized to yield highly reactive monomers suitable for coatings, inks and adhesives. The direct phase transfer epoxidation of squalene and natural rubber was carried out. The modified rubbers undergo facile photocrosslinking in the presence of onium salts to give crosslinked elastomers. 12 refs., 3 figs., 10 tabs.

  19. Towards Effective Photothermal/Photodynamic Treatment Using Plasmonic Gold Nanoparticles.

    Science.gov (United States)

    Bucharskaya, Alla; Maslyakova, Galina; Terentyuk, Georgy; Yakunin, Alexander; Avetisyan, Yuri; Bibikova, Olga; Tuchina, Elena; Khlebtsov, Boris; Khlebtsov, Nikolai; Tuchin, Valery

    2016-01-01

    Gold nanoparticles (AuNPs) of different size and shape are widely used as photosensitizers for cancer diagnostics and plasmonic photothermal (PPT)/photodynamic (PDT) therapy, as nanocarriers for drug delivery and laser-mediated pathogen killing, even the underlying mechanisms of treatment effects remain poorly understood. There is a need in analyzing and improving the ways to increase accumulation of AuNP in tumors and other crucial steps in interaction of AuNPs with laser light and tissues. In this review, we summarize our recent theoretical, experimental, and pre-clinical results on light activated interaction of AuNPs with tissues and cells. Specifically, we discuss a combined PPT/PDT treatment of tumors and killing of pathogen bacteria with gold-based nanocomposites and atomic clusters, cell optoporation, and theoretical simulations of nanoparticle-mediated laser heating of tissues and cells. PMID:27517913

  20. Cation Effect on Copper Chemical Mechanical Polishing

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; LIU Bo; SONG Zhi-Tang; FENG Song-Lin

    2009-01-01

    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demon-strates the worst performance. These results reveal a mechanism that sma//molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  1. Clustering experiments

    CERN Document Server

    Wang, Zhengwei; Tan, Ken; Di, Zengru; Roehner, Bertrand M

    2011-01-01

    It is well known that bees cluster together in cold weather, in the process of swarming (when the ``old'' queen leaves with part of the colony) or absconding (when the queen leaves with all the colony) and in defense against intruders such as wasps or hornets. In this paper we describe a fairly different clustering process which occurs at any temperature and independently of any special stimulus or circumstance. As a matter of fact, this process is about four times faster at 28 degree Celsius than at 15 degrees. Because of its simplicity and low level of ``noise'' we think that this phenomenon can provide a means for exploring the strength of inter-individual attraction between bees or other living organisms. For instance, and at first sight fairly surprisingly, our observations showed that this attraction does also exist between bees belonging to different colonies. As this study is aimed at providing a comparative perspective, we also describe a similar clustering experiment for red fire ants.

  2. Mesoporous Silica Based Gold Catalysts: Novel Synthesis and Application in Catalytic Oxidation of CO and Volatile Organic Compounds (VOCs

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2013-10-01

    Full Text Available Gold nanoparticles, particularly with the particle size of 2–5 nm, have attracted increasing research attention during the past decades due to their surprisingly high activity in CO and volatile organic compounds (VOCs oxidation at low temperatures. In particular, CO oxidation below room temperature has been extensively studied on gold nanoparticles supported on several oxides (TiO2, Fe2O3, CeO2, etc.. Recently, mesoporous silica materials (such as SBA-15, MCM-41, MCM-48 and HMS possessing ordered channel structures and suitable pore diameters, large internal surface areas, thermal stabilities and excellent mechanical properties, have been investigated as suitable hosts for gold nanoparticles. In this review we highlight the development of novel mesoporous silica based gold catalysts based on examples, mostly from recently reported results. Several synthesis methods are described herein. In detail we report: the modification of silica with organic functional groups; the one-pot synthesis with the incorporation of both gold and coupling agent containing functionality for the synthesis of mesoporous silica; the use of cationic gold complexes; the synthesis of silica in the presence of gold colloids or the dispersion of gold colloids protected by ligands or polymers onto silica; the modification of silica by other metal oxides; other conventional preparation methods to form mesoporous silica based gold catalysts. The gold based catalysts prepared as such demonstrate good potential for use in oxidation of CO and VOCs at low temperatures. From the wide family of VOCs, the oxidation of methanol and dimethyldisulfide has been addressed in the present review.

  3. Support-induced Catalytic Activity of Gold Nanocluster

    Science.gov (United States)

    Zhang, Chun; Yoon, Bokwon; Landman, Uzi

    2007-03-01

    The catalytic activity of gold nanoclusters supported on metal-oxide surfaces is a topic of active research efforts. Recently, a dimensionality crossover of gold clusters, adsorbed on a metal-supported thin film of MgO(100), has been predicted^1. We present here a first- principles study of the catalytic activity of a planer Au20 cluster on two- layer MgO(100) film supported by a Mo surface. Both Langmuir-Hinshelwood (LH) and Eley--Rideal (ER) mechanisms of CO oxidation are investigated. The barrier of the LH mechanism is found to be 0.15 eV. For the ER mechanism, the barrier depends on the direction of approach of the CO molecule to the preadsorbed oxygen molecule, varying between a vanishing barrier height and 0.2 eV. Charge transfer from the Mo surface to the cluster supported on the thin MgO(100) film plays a key role in the catalyzed CO oxidation process.

  4. Influence of α-amylase template concentration on systematic entrapment of highly stable and monodispersed colloidal gold nanoparticles

    Science.gov (United States)

    Ananth, A. Nitthin; Ananth, A. Nimrodh; Jose, Sujin P.; Umapathy, S.; Mathavan, T.

    2016-01-01

    Nano gold / α-amylase colloidal dispersions of profound stability were made using simple procedure with a conventional reducing agent. The surface plasmon resonance of the gold nanocrystals was used to quantify the extent of the dispersion stability and functionalization. It is found that the reduced gold nanoparticles were trapped into the protein network without denaturation the structure of α-amylase protein. This kind of entrapment of particles into the protein network prevents clustering of individual gold nanoparticles (6.42 nm ± 0.92 nm) by acting as a natural spacer. Systematic entrapment was facilitated by the affinity of gold to the sulfur moieties (Au-S) in the protein structure.

  5. Influence of α-amylase template concentration on systematic entrapment of highly stable and monodispersed colloidal gold nanoparticles

    Directory of Open Access Journals (Sweden)

    A. Nitthin Ananth

    2016-01-01

    Full Text Available Nano gold / α-amylase colloidal dispersions of profound stability were made using simple procedure with a conventional reducing agent. The surface plasmon resonance of the gold nanocrystals was used to quantify the extent of the dispersion stability and functionalization. It is found that the reduced gold nanoparticles were trapped into the protein network without denaturation the structure of α-amylase protein. This kind of entrapment of particles into the protein network prevents clustering of individual gold nanoparticles (6.42 nm ± 0.92 nm by acting as a natural spacer. Systematic entrapment was facilitated by the affinity of gold to the sulfur moieties (Au-S in the protein structure.

  6. Factor PD-Clustering

    OpenAIRE

    Gettler Summa, Mireille; Palumbo, Francesco; Tortora, Cristina

    2012-01-01

    Factorial clustering methods have been developed in recent years thanks to the improving of computational power. These methods perform a linear transformation of data and a clustering on transformed data optimizing a common criterion. Factorial PD-clustering is based on Probabilistic Distance clustering (PD-clustering). PD-clustering is an iterative, distribution free, probabilistic, clustering method. Factor PD-clustering make a linear transformation of original variables into a reduced numb...

  7. Annealing relaxation of ultrasmall gold nanostructures

    Science.gov (United States)

    Chaban, Vitaly

    2015-01-01

    Except serving as an excellent gift on proper occasions, gold finds applications in life sciences, particularly in diagnostics and therapeutics. These applications were made possible by gold nanoparticles, which differ drastically from macroscopic gold. Versatile surface chemistry of gold nanoparticles allows coating with small molecules, polymers, biological recognition molecules. Theoretical investigation of nanoscale gold is not trivial, because of numerous metastable states in these systems. Unlike elsewhere, this work obtains equilibrium structures using annealing simulations within the recently introduced PM7-MD method. Geometries of the ultrasmall gold nanostructures with chalcogen coverage are described at finite temperature, for the first time.

  8. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    Energy Technology Data Exchange (ETDEWEB)

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1996-12-31

    The problems associated with the disposal of toxic metals in an environmentally acceptable manner continues to plague industry. Such metals as nickel, vanadium, molybdenum, cobalt, iron, and antimony present physiological and ecological challenges that are best addressed through minimization of exposure and dispersion. A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  9. Phage based green chemistry for gold ion reduction and gold retrieval.

    Science.gov (United States)

    Setyawati, Magdiel I; Xie, Jianping; Leong, David T

    2014-01-22

    The gold mining industry has taken its toll on the environment, triggering the development of more environmentally benign processes to alleviate the waste load release. Here, we demonstrate the use of bacteriophages (phages) for biosorption and bioreduction of gold ions from aqueous solution, which potentially can be applied to remediate gold ions from gold mining waste effluent. Phage has shown a remarkably efficient sorption of gold ions with a maximum gold adsorption capacity of 571 mg gold/g dry weight phage. The product of this phage mediated process is gold nanocrystals with the size of 30-630 nm. Biosorption and bioreduction processes are mediated by the ionic and covalent interaction between gold ions and the reducing groups on the phage protein coat. The strategy offers a simple, ecofriendly and feasible option to recover of gold ions to form readily recoverable products of gold nanoparticles within 24 h. PMID:24359519

  10. Thermal Dihydrogen Activation by a Closed-Shell AuCeO2(+) Cluster.

    Science.gov (United States)

    Meng, Jing-Heng; He, Sheng-Gui

    2014-11-01

    Laser-ablation-generated AuCeO2(+) and CeO2(+) oxide clusters were mass-selected using a quadrupole mass filter and reacted with H2 in an ion trap reactor at ambient conditions. The reactions were characterized by mass spectrometry and density functional theory calculations. The gold-cerium bimetallic oxide cluster AuCeO2(+) is more reactive in H2 activation than the pure cerium oxide cluster CeO2(+). The gold atom is the active adsorption site and facilitates the heterolytic cleavage of H2 in collaboration with the separated O(2-) ion of the CeO2 support. To the best of our knowledge, this is the first example of thermal H2 activation by a closed-shell atomic cluster, which provides molecular-level insights into the single gold atom catalysis over metal oxide supports. PMID:26278765

  11. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.;

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural and...

  12. Sorption of alkylammonium cations on montmorillonite

    Czech Academy of Sciences Publication Activity Database

    Navrátilová, Z.; Wojtowicz, P.; Vaculíková, Lenka; Šugárková, Věra

    2007-01-01

    Roč. 4, 3/147/ (2007), s. 59-65. ISSN 1214-9705 R&D Projects: GA ČR GA205/05/0871 Institutional research plan: CEZ:AV0Z30860518 Keywords : montmorillonite * adsorption * alkylammonium cations Subject RIV: CB - Analytical Chemistry, Separation

  13. Cationic flotation of some lithium ores

    International Nuclear Information System (INIS)

    The cationic flotation of some lithium ores (spodumene, amblygonite, petalite, lepidolite) is studied by the measure of zeta potential and micro-flotation tests in Hallimond tube. The effect of some modifier agents (corn starch, meta sodium silicate) on the lithium flotation is studied. (M.A.C.)

  14. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;

    2003-01-01

    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M alk...

  15. Synthesis and evaluation of polymeric gold glyco-conjugates as anti-cancer agents.

    Science.gov (United States)

    Ahmed, Marya; Mamba, Saul; Yang, Xiao-Hong; Darkwa, James; Kumar, Piyush; Narain, Ravin

    2013-06-19

    The antitumor activity of organo-gold compounds is a focus of research from the past two decades. A variety of gold stabilizing ligands such as vitamins and xanthanes have been prepared and explored for their 'chelating effect' as well as for their antitumor activity. Dithiocarbamates (DTC) compounds and their metallic conjugates have been well explored for their antiproliferative activities. In this study, glycopolymer based DTC-conjugates are prepared by reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequently modified with gold(I) phosphine. These polymer-DTC derivatives and their gold compounds are tested for their in vitro toxicity in both normal and cancer cell lines. The Au(I) phosphine conjugated cationic glycopolymers of 10 kDa and 30 kDa are evaluated for their cytotoxicity profiles using MTT assay. Au(I) compounds are well-known for their mitochondrial toxicity, hence hypoxic cell lines bearing unusually enlarged mitochondria are subjected to these anticancer compounds. It is concluded that these polymeric DTC derivatives and their gold conjugates indeed show higher accumulation as well as cytotoxicity to cancer cells under hypoxic conditions in comparison to the normoxic ones. Hypoxic MCF-7 cells showed significant sensitivity toward the low molecular weight (10 kDa) glycopolymer-Au(I) complexes. PMID:23631753

  16. Absorption, fluorescence and resonance Rayleigh scattering spectral characteristics of interaction of gold nanoparticle with safranine T

    Institute of Scientific and Technical Information of China (English)

    HE Youqiu; LIU Shaopu; LIU Qin; LIU Zhongfang; HU Xiaoli

    2005-01-01

    The interaction between gold nanoparticle and safranine T (ST) has been studied with resonance Rayleigh scattering (RRS) spectra, absorption and fluorescence spectra. In the pH 5 solution, citrate [(H2L)2-] self-assembles on the surface of positively-charged gold nanoparticle, which results in the [(Au)n(H2L)m]x- complex. In other words, one of carboxylate oxygens in (H2L)2- moves inward and combines with gold nanoparticle. The other carboxylate oxygens moves outward to form a supermolecular complex anion with x negative charges. Then by virtue of electrostatic attraction, hydrophobic force and charge transfer action, the complex anion binds with ST cation to form a new ion-association complex. Here (H2L)2- acts as a bridge. The formation of the complex results in the significant enhancement of RRS intensity, the appearance of new RRS spectrum, the red shift of plasma absorption band of gold nanoparticle as well as the decrease in the absorbance and fluorescence quenching for safranine T. In this work, the interaction between gold nanoparticle and ST on the RRS, absorption and fluorescence spectra has been investigated. The reason why RRS intensity increases greatly and the reaction mechanism have been inquired. The results show that RRS spectra can not only be used to study nanoparticle and reaction product, but also are a sensitive means to characterize and detect nanoparticles.

  17. Cluster automorphisms and compatibility of cluster variables

    OpenAIRE

    Assem, Ibrahim; Schiffler, Ralf; Shramchenko, Vasilisa

    2013-01-01

    In this paper, we introduce a notion of unistructural cluster algebras, for which the set of cluster variables uniquely determines the clusters. We prove that cluster algebras of Dynkin type and cluster algebras of rank 2 are unistructural, then prove that if $\\mathcal{A}$ is unistructural or of Euclidean type, then $f: \\mathcal{A}\\to \\mathcal{A}$ is a cluster automorphism if and only if $f$ is an automorphism of the ambient field which restricts to a permutation of the cluster variables. In ...

  18. Globular Cluster Formation in the Virgo Cluster

    CERN Document Server

    Moran, C Corbett; Lake, G

    2014-01-01

    Metal poor globular clusters (MPGCs) are a unique probe of the early universe, in particular the reionization era. Systems of globular clusters in galaxy clusters are particularly interesting as it is in the progenitors of galaxy clusters that the earliest reionizing sources first formed. Although the exact physical origin of globular clusters is still debated, it is generally admitted that globular clusters form in early, rare dark matter peaks (Moore et al. 2006; Boley et al. 2009). We provide a fully numerical analysis of the Virgo cluster globular cluster system by identifying the present day globular cluster system with exactly such early, rare dark matter peaks. A popular hypothesis is that that the observed truncation of blue metal poor globular cluster formation is due to reionization (Spitler et al. 2012; Boley et al. 2009; Brodie & Strader 2006); adopting this view, constraining the formation epoch of MPGCs provides a complementary constraint on the epoch of reionization. By analyzing both the l...

  19. Land cover classification using reformed fuzzy C-means

    Indian Academy of Sciences (India)

    B Sowmya; B Sheelarani

    2011-04-01

    This paper explains the task of land cover classification using reformed fuzzy C means. Clustering is the assignment of objects into groups called clusters so that objects from the same cluster are more similar to each other than objects from different clusters. The most basic attribute for clustering of an image is its luminance amplitude for a monochrome image and colour components for a colour image. Since there are more than 16 million colours available in any given image and it is difficult to analyse the image on all of its colours, the likely colours are grouped together by clustering techniques. For that purpose reformed fuzzy C means algorithm has been used. The segmented images are compared using image quality metrics. The image quality metrics used are peak signal to noise ratio (PSNR), error image and compression ratio. The time taken for image segmentation is also used as a comparison parameter. The techniques have been applied to classify the land cover.

  20. Solid state and aqueous behavior of uranyl peroxide cage clusters

    Science.gov (United States)

    Pellegrini, Kristi Lynn

    Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

  1. Cation-cation interactions, magnetic communication and reactivity of the pentavalent uraniumion [U(NR)2]+

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, Liam P [Los Alamos National Laboratory; Schelter, Eric J [Los Alamos National Laboratory; Boncella, James M [Los Alamos National Laboratory; Yang, Ping [Los Alamos National Laboratory; Gsula, Robyn L [NON LANL; Scott, Brian L [Los Alamos National Laboratory; Thompson, Joe D [Los Alamos National Laboratory; Kiplinger, Jacqueline L [Los Alamos National Laboratory; Batista, Enrique R [Los Alamos National Laboratory

    2009-01-01

    The dimeric bis(imido) uranium complex [{l_brace}U(NtBu)2(I)(tBu2bpy){r_brace}2] (see picture; U green, N blue, I red) has cation-cation interactions between [U(NR)2]+ ions. This f1-f1 system also displays f orbital communication between uranium(V) centers at low temperatures, and can be oxidized to generate uranium(VI) bis(imido) complexes.

  2. Biomass processing over gold catalysts

    CERN Document Server

    Simakova, Olga A; Murzin, Dmitry Yu

    2013-01-01

    The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds

  3. Gold nanotube: structure and melting

    OpenAIRE

    Bilalbegovic, G.

    2002-01-01

    In the process of molecular dynamics simulation studies of gold nanowires an interesting structure is discovered. This is a finite double-wall nanowire with a large empty core similar to single-wall and double-wall carbon nanotubes. The structure of the 16-10 gold nanotube is studied at the room temperature. An investigation of the high-temperature stability has also been carried out. An unusual inward evaporation of atoms from cylindrical liquid walls is found at T>= 1200 K.

  4. Are RCTs the gold standard?

    OpenAIRE

    Cartwright, N.

    2007-01-01

    The claims of randomized controlled trials (RCTs) to be the gold standard rest on the fact that the ideal RCT is a deductive method: if the assumptions of the test are met, a positive result implies the appropriate causal conclusion. This is a feature that RCTs share with a variety of other methods, which thus have equal claim to being a gold standard. This article describes some of these other deductive methods and also some useful non-deductive methods, including the hypothetico-deductive m...

  5. Coalescence Behavior of Gold Nanoparticles

    Directory of Open Access Journals (Sweden)

    Wang YQ

    2009-01-01

    Full Text Available Abstract The tetraoctylammonium bromide (TOAB-stabilized gold nanoparticles have been successfully fabricated. After an annealing of the as-synthesized nanoparticles at 300 °C for 30 min, the coalescence behavior of gold nanoparticles has been investigated using high-resolution transmission electron microscopy in detail. Two types of coalescence, one being an ordered combination of two or more particles in appropriate orientations through twinning, and the other being an ordered combination of two small particles with facets through a common lattice plane, have been observed.

  6. Ultrastable and Biofunctionalizable Gold Nanoparticles.

    Science.gov (United States)

    Gupta, Akash; Moyano, Daniel F; Parnsubsakul, Attasith; Papadopoulos, Alexander; Wang, Li-Sheng; Landis, Ryan F; Das, Riddha; Rotello, Vincent M

    2016-06-01

    Gold nanoparticles provide an excellent platform for biological and material applications due to their unique physical and chemical properties. However, decreased colloidal stability and formation of irreversible aggregates while freeze-drying nanomaterials limit their use in real world applications. Here, we report a new generation of surface ligands based on a combination of short oligo (ethylene glycol) chains and zwitterions capable of providing nonfouling characteristics while maintaining colloidal stability and functionalization capabilities. Additionally, conjugation of these gold nanoparticles with avidin can help the development of a universal toolkit for further functionalization of nanomaterials. PMID:27191946

  7. Nanobubble trouble on gold surfaces

    DEFF Research Database (Denmark)

    Holmberg, Maria; Kuhle, A.; Garnaes, J.;

    2003-01-01

    When analyzing surfaces related to biosensors with in situ atomic force microscopy (AFM), the existence of nanobubbles called for our attention. The bubbles seem to form spontaneously when gold surfaces are immersed in clean water and are probably a general phenomenon at water-solid interfaces....... Besides from giving rise to undesired effects in, for example, biosensors, nanobubbles can also cause artifacts in AFM imaging. We have observed nanobubbles on unmodified gold surfaces, immersed in clean water, using standard silicon AFM probes. Nanobubbles can be made to disappear from contact mode AFM...

  8. Self-assembly and structure of directly imaged inorganic-anion monolayers on a gold nanoparticle.

    Science.gov (United States)

    Wang, Yifeng; Neyman, Alevtina; Arkhangelsky, Elizabeth; Gitis, Vitaly; Meshi, Louisa; Weinstock, Ira A

    2009-12-01

    Cryogenic "trapping" was used to obtain the first TEM images of self-assembled monolayers of inorganic anions on a gold nanoparticle. This unique structural information makes it possible to study the formation of a protecting-ligand shell at an unprecedented level of detail. The protecting ligands are polyoxometalates (POMs; alpha-X(n+)W(12)O(40)((8-n)-), X(n+) = Al(3+) and "2H(+)", and alpha-X(n+)W(11)O(39)((12-n)-), X(n+) = P(5+), Si(4+), and Al(3+)) with large negative charges for association with the gold surface and W atoms (Z = 74) for TEM imaging. The POM-anion shells were obtained by ligand exchange from citrate-protected 13.8 nm gold nanoparticles. Replacement of the organic (citrate) by inorganic (tungsten-oxide) ligand shells results in substantial changes in the surface plasmon resonance (SPR). By correlating cryo-TEM images with changes in the SPR, degrees of surface coverage were reliably quantified by UV-visible spectroscopy. Then, the kinetics and thermodynamics of ligand-shell formation were investigated by systematically varying POM structure and charge. Rates of POM association with the gold surface ("nucleation") are inhibited by the electric-potential barrier of the citrate-stabilized particles, while binding affinities increase linearly with the charges (from 5- to 9-) of structurally different POM anions, suggesting that no single orientation ("lattice matching") is required for monolayer self-assembly. Time-dependent cryo-TEM images reveal that monolayer growth occurs via "islands", a mechanism that points to cation-mediated attraction between bound POMs. Complete ligand shells comprised of 330 molecules of alpha-AlW(11)O(39)(9-) (1) possess small net charges (29e from zeta-potential measurements) and short Debye lengths (kappa(-1) = 1.0 nm), which indicate that approximately 99% of the 2970 K(+) counter cations lie within ca. 1.5 nm (approximately 3 hydrated K(+) ion diameters) from the outer surface of the POM shell. Energetic analysis of

  9. Characterizing the textural features of gold ores for optimizing gold extraction

    Science.gov (United States)

    Hausen, Donald M.

    2000-04-01

    The beneficiation of gold ores begins with an examination and classification of the types of gold occurrences and recovery methods. Measurements can provide the necessary grind size for liberation and determine the sizes and associations of gold with gangue materials. In this article, the textural features several gold occurrences are described and compared.

  10. 197Au Moessbauer study of gold ores, mattes, roaster products, and gold minerals

    International Nuclear Information System (INIS)

    The chemical state of gold in gold ores, mattes and roaster products has been studied by 197Au Moessbauer spectroscopy. Gold minerals were studied in order to provide reference data for the ore spectra. 57Fe Moessbauer spectroscopy was used to monitor the iron-compounds always present in gold ores and to follow their transformations caused by smelting and roasting. (orig.)

  11. Gibson's Paradox and the Gold Standard

    OpenAIRE

    Robert B. Barsky; Summers, Lawrence H.

    1985-01-01

    This paper provides a new explanation for Gibson's Paradox -- the observation that the price level and the nominal interest rate were positively correlated over long periods of economic history. We explain this phenomenon interms of the fundamental workings of a gold standard. Under a gold standard, the price level is the reciprocal of the real price of gold. Because gold is adurable asset, its relative price is systematically affected by fluctuations inthe real productivity of capital, which...

  12. Minerals in Afghanistan : the potential for gold

    OpenAIRE

    Benham, Antony John; Coats, Stan

    2006-01-01

    Gold has been worked in Afghanistan for centuries from many areas including Takhar province in the north and from Ghazni, Zabul, and Kandahar provinces in the south-west of the country. Currently, gold is produced almost solely by artisanal miners working the Samti Placer Deposit in Takhar Province. Gold deposits and prospects are known in rocks of Proterozoic to Neogene age. Many styles of gold mineralisation occur, in particular skarn, vein-hosted, porphyry and alluvial...

  13. Adaptive Evolutionary Clustering

    OpenAIRE

    Xu, Kevin S.; Kliger, Mark; Hero III, Alfred O.

    2011-01-01

    In many practical applications of clustering, the objects to be clustered evolve over time, and a clustering result is desired at each time step. In such applications, evolutionary clustering typically outperforms traditional static clustering by producing clustering results that reflect long-term trends while being robust to short-term variations. Several evolutionary clustering algorithms have recently been proposed, often by adding a temporal smoothness penalty to the cost function of a st...

  14. Relational visual cluster validity

    OpenAIRE

    Ding, Y.; Harrison, R F

    2007-01-01

    The assessment of cluster validity plays a very important role in cluster analysis. Most commonly used cluster validity methods are based on statistical hypothesis testing or finding the best clustering scheme by computing a number of different cluster validity indices. A number of visual methods of cluster validity have been produced to display directly the validity of clusters by mapping data into two- or three-dimensional space. However, these methods may lose too much information to corre...

  15. Linker-mediated assembly of gold nanoparticles into multimeric motifs

    Science.gov (United States)

    Sikora, Mateusz; Szymczak, Piotr; Thompson, Damien; Cieplak, Marek

    2011-11-01

    We present a theoretical description of linker-mediated self-assembly of gold nanoparticles (Au-NP). Using mesoscale simulations with a coarse-grained model for the Au NPs and dirhenium-based linker molecules, we investigate the conditions under which large clusters can grow and construct a phase diagram that identifies favorable growth conditions in terms of floating and bound linker concentrations. The findings can be considered as generic, as we expect other NP-linker systems to behave in a qualitatively similar way. In particular, we also discuss the case of antibody-functionalised Au NPs connected by the C-reactive proteins (CRPs). We extract some general rules for NP linking that may aid the production of size- and shape-specific NP clusters for technology applications.

  16. Linker-mediated assembly of gold nanoparticles into multimeric motifs

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, Mateusz; Cieplak, Marek [Institute of Physics, Polish Academy of Sciences, Aleja Lotnikow 32/46, 02-668 Warsaw (Poland); Szymczak, Piotr [Institute of Theoretical Physics, Faculty of Physics, University of Warsaw, ulica Hoza 69, 00-681 Warsaw (Poland); Thompson, Damien, E-mail: mc@ifpan.edu.pl [Tyndall National Institute, Lee Maltings, University College Cork, Cork (Ireland)

    2011-11-04

    We present a theoretical description of linker-mediated self-assembly of gold nanoparticles (Au-NP). Using mesoscale simulations with a coarse-grained model for the Au NPs and dirhenium-based linker molecules, we investigate the conditions under which large clusters can grow and construct a phase diagram that identifies favorable growth conditions in terms of floating and bound linker concentrations. The findings can be considered as generic, as we expect other NP-linker systems to behave in a qualitatively similar way. In particular, we also discuss the case of antibody-functionalised Au NPs connected by the C-reactive proteins (CRPs). We extract some general rules for NP linking that may aid the production of size- and shape-specific NP clusters for technology applications.

  17. Metallic gold beads in hyaluronic acid

    DEFF Research Database (Denmark)

    Pedersen, Dan Sonne; Tran, Thao Phuong; Smidt, Kamille;

    2013-01-01

    exploiting macrophage-induced liberation of gold ions (dissolucytosis) from gold surfaces. Injecting gold beads in hyaluronic acid (HA) as a vehicle into the cavities of the brain can delay clinical signs of disease progression in the MS model, experimental autoimmune encephalitis (EAE). This study...... effects of hyaluronic acid....

  18. Kinetics of cyaniding of gold comprising ores

    International Nuclear Information System (INIS)

    Present article is devoted to kinetics of cyaniding process of gold comprising ores. Thus in laboratory conditions the researches on leaching of gold and silver from ores of various deposits of Tajikistan by means of cyaniding were conducted. The results of laboratory researches on cyaniding of ores of various deposits are presented. The flowsheet of cyaniding of gold comprising ores was elaborated.

  19. Stability of gold cages (Au16 and Au17) at finite temperature

    Indian Academy of Sciences (India)

    Prachi Chandrachud; Kavita Joshi; Sailaja Krishnamurty; D G Kanhere

    2009-05-01

    We have employed ab initio molecular dynamics to investigate the stability of the smallest gold cages, namely Au16 and Au17, at finite temperatures. First, we obtain the ground state structure along with at least 50 distinct isomers for both the clusters. This is followed by the finite temperature simulations of these clusters. Each cluster is maintained at 12 different temperatures for a time period of at least 150 ps. Thus, the total simulation time is of the order of 2.4 ns for each cluster. We observe that the cages are stable at least up to 850 K. Although both clusters melt around the same temperature, i.e. around 900 K, Au17 shows a peak in the heat capacity curve in contrast to the broad peak seen for Au16.

  20. Facile Synthesis of Gd-Functionalized Gold Nanoclusters as Potential MRI/CT Contrast Agents

    OpenAIRE

    Wenjun Le; Shaobin Cui; Xin Chen; Huanhuan Zhu; Bingdi Chen; Zheng Cui

    2016-01-01

    Multi-modal imaging plays a key role in the earlier detection of disease. In this work, a facile bioinspired method was developed to synthesize Gd-functionalized gold nanoclusters (Gd-Au NCs). The Gd-Au NCs exhibit a uniform size, with an average size of 5.6 nm in dynamic light scattering (DLS), which is a bit bigger than gold clusters (3.74 nm, DLS), while the fluorescent properties of Gd-Au NCs are almost the same as that of Au NCs. Moreover, the Gd-Au NCs exhibit a high longitudinal relaxi...

  1. A Simple Approach to Control the Growth of Non-spherical Gold Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Hong YUAN; Ru Xiu CAI; Dai Wen PANG

    2003-01-01

    A simple method to prepare the non-spherical gold particles was developed. The result solution included trigonal, truncated trigonal, hexagonal layers, and a pseudo-pentagonal shaped gold nanocrystals. The key factor is to control the relative rates of nucleation and cluster growth in this method. These attributes make seeding growth method as a useful tool in the fabrication of colloidal metal materials. A longitudinal plasmon resonance of 866 nm was observed, which is in the near-IR spectral regions (600-1000 nm). The excellent optical properties as near-IR labels are used to develop highly sensitive analysis method.

  2. Excited States of Gold(I) Compounds, Luminescence and Gold-Gold Bonding

    OpenAIRE

    Fackler, John P.Jr.; Assefa, Zerihun; Forward, Jennifer M.; Staples, Richard J.

    1994-01-01

    It has long been established by Khan that the superoxide anion, O2 -, generates singlet oxygen, O2 1Δg, during dismutation. Auranofin, gold-phosphine thiols, β-Carotene, and metal-sulfur compounds can rapidly quench singlet O2. The quenching of the O2 1Δg, which exists at 7752 cm-1 above the ground state triplet, may be due to the direct interaction of the singlet O2 with gold(I) or may require special ligands such as those containing sulfur coordinated to the metal. Thus we have been examini...

  3. Gold in Pyrite within Altai – Sayan Folded Belt Gold Deposits

    International Nuclear Information System (INIS)

    This article describes the result analysis of gold in pyrite for a number of some Altai – Sayan folded belt gold deposits. The analyzed pyrite samples showed gold grade from 0.04 to 20.0 g/t., which proves the fact that the gold concentrations in pyrites is irregular. Pyrites in productive mineral associations include significant metal enrichment, while pyrites of early poor gold-bearing associations and wallrock metasomatites are less prolific

  4. Gold Dreams, Gold Nightmares: The Social Construction of Inflation as Delegitimation Discourse

    OpenAIRE

    Adam Rafalovich

    2011-01-01

    Using archival data from the four most popular gold investment websites, this study is a content analysis of gold investment enthusiast ('gold bug') commentaries over a six-month time period, from November 2007 to April 2008. We examine gold bug discourse as a conspiracy narrative whose central tenet is the criticism of inflationary monetary policy. Gold bugs argue that the continual presence of inflation demonstrates the fundamental flaws of global capitalism and the illegitimacy of the admi...

  5. Structurally Distinct Cation Channelrhodopsins from Cryptophyte Algae.

    Science.gov (United States)

    Govorunova, Elena G; Sineshchekov, Oleg A; Spudich, John L

    2016-06-01

    Microbial rhodopsins are remarkable for the diversity of their functional mechanisms based on the same protein scaffold. A class of rhodopsins from cryptophyte algae show close sequence homology with haloarchaeal rhodopsin proton pumps rather than with previously known channelrhodopsins from chlorophyte (green) algae. In particular, both aspartate residues that occupy the positions of the chromophore Schiff base proton acceptor and donor, a hallmark of rhodopsin proton pumps, are conserved in these cryptophyte proteins. We expressed the corresponding polynucleotides in human embryonic kidney (HEK293) cells and studied electrogenic properties of the encoded proteins with whole-cell patch-clamp recording. Despite their lack of residues characteristic of the chlorophyte cation channels, these proteins are cation-conducting channelrhodopsins that carry out light-gated passive transport of Na(+) and H(+). These findings show that channel function in rhodopsins has evolved via multiple routes. PMID:27233115

  6. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  7. Mechanism of adsorption of cations onto rocks

    International Nuclear Information System (INIS)

    Adsorption behavior of cations onto granite was investigated. The distribution coefficient (Kd) of Sr2+ and Ba2+ onto granite was determined in the solution of which pH was ranged from 3.5 to 11.3 and ionic strength was set at 10-2 and 10-1. The Kd values were found to increase with increasing pH and with deceasing ionic strength. The obtained data were successfully analyzed by applying an electrical double layer model. The optimum parameter values of the double layer electrostatics and adsorption reactions were obtained, and the mechanism of adsorption of cations onto granite was discussed. Feldspar was found to play an important role in their adsorption. (author)

  8. Planar Chiral, Ferrocene-Stabilized Silicon Cations.

    Science.gov (United States)

    Schmidt, Ruth K; Klare, Hendrik F T; Fröhlich, Roland; Oestreich, Martin

    2016-04-01

    The preparation of a series of planar chiral, ferrocenyl-substituted hydrosilanes as precursors of ferrocene-stabilized silicon cations is described. These molecules also feature stereogenicity at the silicon atom. The generation and (29) Si NMR spectroscopic characterization of the corresponding silicon cations is reported, and problems arising from interactions of the electron-deficient silicon atom and adjacent C(sp(3) )-H bonds or aromatic π donors are discussed. These issues are overcome by tethering another substituent at the silicon atom to the ferrocene backbone. The resulting annulation also imparts conformational rigidity and steric hindrance in such a way that the central chirality at the silicon atom is set with complete diastereocontrol. These chiral Lewis acid catalysts were then tested in difficult Diels-Alder reactions, but no enantioinduction was seen. PMID:26929105

  9. Ultrafast dynamics of water in cationic micelles.

    Science.gov (United States)

    Dokter, Adriaan M; Woutersen, Sander; Bakker, Huib J

    2007-03-28

    The effect of confinement on the dynamical properties of liquid water is investigated for water enclosed in cationic reverse micelles. The authors performed mid-infrared ultrafast pump-probe spectroscopy on the OH-stretch vibration of isotopically diluted HDO in D(2)O in cetyltrimethylammonium bromide (CTAB) reverse micelles of various sizes. The authors observe that the surfactant counterions are inhomogeneously distributed throughout the reverse micelle, and that regions of extreme salinity occur near the interfacial Stern layer. The authors find that the water molecules in the core of the micelles show similar orientational dynamics as bulk water, and that water molecules in the counterion-rich interfacial region are much less mobile. An explicit comparison is made with the dynamics of water confined in anionic sodium bis(2-ethythexyl) sulfosuccinate (AOT) reverse micelles. The authors find that interfacial water in cationic CTAB reverse micelles has a higher orientational mobility than water in anionic AOT reverse micelles. PMID:17411144

  10. Ultrafast dynamics of water in cationic micelles

    Science.gov (United States)

    Dokter, Adriaan M.; Woutersen, Sander; Bakker, Huib J.

    2007-03-01

    The effect of confinement on the dynamical properties of liquid water is investigated for water enclosed in cationic reverse micelles. The authors performed mid-infrared ultrafast pump-probe spectroscopy on the OH-stretch vibration of isotopically diluted HDO in D2O in cetyltrimethylammonium bromide (CTAB) reverse micelles of various sizes. The authors observe that the surfactant counterions are inhomogeneously distributed throughout the reverse micelle, and that regions of extreme salinity occur near the interfacial Stern layer. The authors find that the water molecules in the core of the micelles show similar orientational dynamics as bulk water, and that water molecules in the counterion-rich interfacial region are much less mobile. An explicit comparison is made with the dynamics of water confined in anionic sodium bis(2-ethythexyl) sulfosuccinate (AOT) reverse micelles. The authors find that interfacial water in cationic CTAB reverse micelles has a higher orientational mobility than water in anionic AOT reverse micelles.

  11. Optical trapping of gold aerosols

    DEFF Research Database (Denmark)

    Schmitt, Regina K.; Pedersen, Liselotte Jauffred; Taheri, S. M.;

    2015-01-01

    Aerosol trapping has proven challenging and was only recently demonstrated.1 This was accomplished by utilizing an air chamber designed to have a minimum of turbulence and a laser beam with a minimum of aberration. Individual gold nano-particles with diameters between 80 nm and 200 nm were trappe...

  12. Gold color in dental alloys.

    Science.gov (United States)

    Cameron, T

    1997-01-01

    This article will help the dental laboratory with alloy selection by exploring how the relationship among color, ductility and strength applies to gold and how color can be quantified. Because higher quality materials translate into higher profits, upselling to the dentist and patient is also discussed. PMID:9524484

  13. Gold Medals and Overall Health

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The 16th Asian Games concluded on November 27 in south China’s Guangzhou, Guangdong Province. The Chinese delegation set new records, with its number of gold medals and total medals, both far more than any other Asian countries and regions.

  14. Proton dynamics investigation for dimethyl ammonium cation

    International Nuclear Information System (INIS)

    Proton dynamics in dimethyl ammonium cation has been investigated by means of NMR and spin echo methods in polycrystalline salts [NH2(CH3)2]+Bi2J9- and [NH2(CH3)2]+SbJ9-. Spin-lattice relaxation time as well as second moment of NMR line have been measured for influence study of crystal structure changes on proton dynamics

  15. Alkaline earth cation extraction from acid solution

    Science.gov (United States)

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  16. Rabbit cationic protein enhances leukocyte adhesiveness.

    OpenAIRE

    Oseas, R S; Allen, J; Yang, H. H.; Baehner, R. L.; Boxer, L A

    1981-01-01

    Cationic protein purified from rabbit peritoneal polymorphonuclear leukocytes (PMN) was demonstrated to incite autoaggregation of the rabbit PMN and promote adhesiveness of human PMN to endothelial cells. PMN aggregation induced by supernatants derived from secretory PMN was blocked by a specific anticationic protein antibody. These studies reveal that a positively charged protein derived from the PMN can alter surface properties of the PMN itself and imply a role for this protein in PMN immo...

  17. Limited data speaker identification

    Indian Academy of Sciences (India)

    H S Jayanna; S R Mahadeva Prasanna

    2010-10-01

    In this paper, the task of identifying the speaker using limited training and testing data is addressed. Speaker identification system is viewed as four stages namely, analysis, feature extraction, modelling and testing. The speaker identification performance depends on the techniques employed in these stages. As demonstrated by different experiments, in case of limited training and testing data condition, owing to less data, existing techniques in each stage will not provide good performance. This work demonstrates the following: multiple frame size and rate (MFSR) analysis provides improvement in the analysis stage, combination of mel frequency cepstral coefficients (MFCC), its temporal derivatives $(\\Delta,\\Delta \\Delta)$, linear prediction residual (LPR) and linear prediction residual phase (LPRP) features provides improvement in the feature extraction stage and combination of learning vector quantization (LVQ) and gaussian mixture model – universal background model (GMM–UBM) provides improvement in the modelling stage. The performance is further improved by integrating the proposed techniques at the respective stages and combining the evidences from them at the testing stage. To achieve this, we propose strength voting (SV), weighted borda count (WBC) and supporting systems (SS) as combining methods at the abstract, rank and measurement levels, respectively. Finally, the proposed hierarchical combination (HC) method integrating these three methods provides significant improvement in the performance. Based on these explorations, this work proposes a scheme for speaker identification under limited training and testing data.

  18. Low cation coordination in oxide melts

    Energy Technology Data Exchange (ETDEWEB)

    Skinner, Lawrie [State University of New York, Stony Brook; Benmore, Chris J [Argonne National Laboratory (ANL); Du, Jincheng [University of North Texas; Weber, Richard [Argonne National Laboratory (ANL); Neuefeind, Joerg C [ORNL; Tumber, Sonia [Materials Development, Inc., Evanston, IL; Parise, John B [Stony Brook University (SUNY)

    2014-01-01

    The complete set of Faber-Ziman partial pair distribution functions for a rare earth oxide liquid were measured for the first time by combining aerodynamic levitation, neutron diffraction, high energy x-ray diffraction and isomorphic substitution using Y2 O3 and Ho2 O3 melts. The average Y- O coordination is measured to be 5.5(2), which is significantly less than the octahedral coordination of crystalline Y2 O3 (or Ho2 O3 ). Investigation of high temperature La2 O3 , ZrO2 , SiO2 , and Al2 O3 melts by x-ray diffraction and molecular dynamics simulations also show lower-than-crystal cation- oxygen coordination. These measurements suggest a general trend towards lower M-O coordination compared to their crystalline counterparts. It is found that this coordination number drop is larger for lower field strength, larger radius cations and is negligible for high field strength (network forming) cations. These findings have broad implications for predicting the local structure and related physical properties of metal-oxide melts and oxide glasses.

  19. Cation-Exchange Equilibria with Fused Salts

    International Nuclear Information System (INIS)

    Solute distributions of alkali metal, alkaline- earth, transition metal, and actinide ions have been studied in fused salt-cation exchanger systems. The fused salts employed were alkali halides and nitrates. The cation exchangers used were natural zeolites, synthetic zeolites, high-porosity glasses, and molten oxide mixtures. The molten exchangers were composed of Na2O and B2O3 in various proportions. The relative quantities not only determined the exchanger capacity and electrolyte penetration but also produced distribution coefficients for a given solute which varied over several orders of magnitude. Moreover, they produced marked reversals in the selectivity series. Additional studies on the anion distributions, miscibility diagrams, vapour pressures and diffusion rates in these systems have elucidated the mechanisms involved and the relation of selectivity to solute properties, system thermodynamics, exchanger structure and available functional groups. In the region of high Na2O composition, the distribution coefficients for mono-, di- and trivalent cations in NaCl have not only the same order of selectivity found in Dowex 50-HCl systems but also similar values for the distribution coefficients. The results are summarized qualitatively and compared to behaviour in aqueous systems (Table VII). (author)

  20. [Biosynthesis of gold nanoparticles by Azospirillum brasilense].

    Science.gov (United States)

    Kupriashina, M A; Vetchinkina, E P; Burov, A M; Ponomareva, E G; Nikitina, V E

    2014-01-01

    Plant-associated nitrogen-fixing soil bacteria Azospirillum brasilense were shown to reduce the gold of chloroauric acid to elemental gold, resulting in formation of gold nanoparicles. Extracellular phenoloxidizing enzymes (laccases and Mn peroxidases) were shown to participate in reduction of Au+3 (HAuCl4) to Au(0). Transmission electron microscopy revealed accumulation of colloidal gold nanoparticles of diverse shape in the culture liquid of A. brasilense strains Sp245 and Sp7. The size of the electron-dense nanospheres was 5 to 50 nm, and the size of nanoprisms varied from 5 to 300 nm. The tentative mechanism responsible for formation of gold nanoparticles is discussed. PMID:25423733

  1. 16 CFR Appendix to Part 23 - Exemptions Recognized in the Assay for Quality of Gold Alloy, Gold Filled, Gold Overlay, Rolled...

    Science.gov (United States)

    2010-01-01

    ... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Exemptions Recognized in the Assay for...—Exemptions Recognized in the Assay for Quality of Gold Alloy, Gold Filled, Gold Overlay, Rolled Gold Plate... in any assay for quality of a karat gold industry product include springs, posts, and separable...

  2. Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

    Science.gov (United States)

    Abdellatif, M. H.; Ghosh, S.; Liakos, I.; Scarpellini, A.; Marras, S.; Diaspro, A.; Salerno, M.

    2016-02-01

    The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.

  3. [Antioxidant activity of cationic whey protein isolate].

    Science.gov (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A

    2012-01-01

    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pwhey protein isolate has an

  4. Synthesis, purification and assembly of gold and iron oxide nanoparticles

    Science.gov (United States)

    Qiu, Penghe

    , 6 & 7), nanoparticles were assembled into three different hierachical structures through both template-assisted and template-free approaches. In the template-assisted assembly, gold nanorods were aligned into ordered 1D linear pattern by using soft biological filamentous, namely bacteria flagella, as templates. Two different ways of assembling nanorods onto flagella were investigated. In another study, a highly commercialized polymer, polyvinylpyrrolidone (PVP), was discovered for the first time to be able to self-assemble into branched hollow fibers. Based on this discovery, two approaches (one through direct deposition of silica onto the PVP aggregate and the other through co-assembly of PVP covered gold nanoparticles with free PVP molecules) by which the self-assembly behavior of PVP could be exploited to template the formation of branched hollow inorganic fibers were demonstrated. In the template-free assembly, a general method for assembling nanoparticle into clusters (NPCs) in an oil-in-water emulsion system was investigated. Detailed studies on the mechanism of formation of NPCs structure, optimized conditions, scalable production and surface chemistry manipulation were carried out. Besides, comparison of the properties of individual and clustered iron oxide nanoparticles was conducted. It was discovered that due to their collective properties, NPCs are more responsive to an external magnetic field and can potentially serve as better contrast enhancement agents than individually dispersed magnetic NPs in Magnetic Resonance Imaging (MRI).

  5. Entropy-Driven Clustering in Tetrahedrally Bonded Multinary Materials

    Science.gov (United States)

    Zawadzki, Paweł; Zakutayev, Andriy; Lany, Stephan

    2015-03-01

    Compositional inhomogeneities in multielemental materials typically form due to lowering of the energy relative to the homogeneous phase. Here, we demonstrate an entropy-driven mechanism in the zinc-blende derived cation-substituted multinary compounds Cu2SnS3 (CTS) and Cu2ZnSnS4 (CZTS). Using a motif-based model Hamiltonian and Monte Carlo simulations, we find that disorder leads to a redistribution of the structural motifs in such a way to create cation clustering. The associated formation of (sub-) nanometer-scale compositional inhomogeneities can cause potential fluctuations with detrimental consequences for photovoltaic applications.

  6. Leaching behavior of butanedionedioxime as gold ligand

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Butanedionedioxime, a small organic compound with low-toxicity and good chemical stability, has been proposed as an effective gold ligand in gold extraction. The result of experiment shows that: 1) highly effective gold lixiviantcan be composed of butanedionedioxime (BDM) with many oxidants, especially potassium permanganate; 2)in the leaching system of BD M- K M nO4 the suitable Ox/Lig(ratio of oxidants to gold ligands) tange is 0.20 ~ 0. 50, optimally 0.25 ~0.45 at the pH range of 7 ~ 11; 3) BDM-KMnO4 extraction of gold from an oxide ore is similar to cyanide(cyanide-O2)extraction, but the leaching rate of gold by BDM-KMnO4 is faster than that by cyanide-O2; 4) gold may readily be recov-ered by carbon adsorption and zinc precipitation

  7. Cation distribution and mixing thermodynamics in Fe/Ni thiospinels

    Science.gov (United States)

    Haider, Saima; Grau-Crespo, Ricardo; Devey, Antony J.; de Leeuw, Nora H.

    2012-07-01

    The structural analogy between Ni-doped greigite minerals (Fe3S4) and the (Fe, Ni)S clusters present in biological enzymes has led to suggestions that these minerals could have acted as catalysts for the origin of life. However, little is known about the distribution and stability of Ni dopants in the greigite structure. We present here a theoretical investigation of mixed thiospinels (Fe1-xNix)3S4, using a combination of density functional theory (DFT) calculations and Monte Carlo simulations. We find that the equilibrium distribution of the cations deviates significantly from a random distribution: at low Ni concentrations, Ni dopants are preferably located in octahedral sites, while at higher Ni concentrations the tetrahedral sites become much more favourable. The thermodynamic mixing behaviour between greigite and polydymite (Ni3S4) is dominated by the stability field of violarite (FeNi2S4), for which the mixing enthalpy exhibits a deep negative minimum. The analysis of the free energy of mixing shows that Ni doping of greigite is very unstable with respect to the formation of a separate violarite phase. The calculated variation of the cubic cell parameter with composition is found to be non-linear, exhibiting significant deviation from Vegard’s law, but in agreement with experiment.

  8. Partitional clustering algorithms

    CERN Document Server

    2015-01-01

    This book summarizes the state-of-the-art in partitional clustering. Clustering, the unsupervised classification of patterns into groups, is one of the most important tasks in exploratory data analysis. Primary goals of clustering include gaining insight into, classifying, and compressing data. Clustering has a long and rich history that spans a variety of scientific disciplines including anthropology, biology, medicine, psychology, statistics, mathematics, engineering, and computer science. As a result, numerous clustering algorithms have been proposed since the early 1950s. Among these algorithms, partitional (nonhierarchical) ones have found many applications, especially in engineering and computer science. This book provides coverage of consensus clustering, constrained clustering, large scale and/or high dimensional clustering, cluster validity, cluster visualization, and applications of clustering. Examines clustering as it applies to large and/or high-dimensional data sets commonly encountered in reali...

  9. Small angle neutron scattering studies on the interaction of cationic surfactants with bovine serum albumin

    Indian Academy of Sciences (India)

    Nuzhat Gull; S Chodankar; V K Aswal; Kabir-Ud-Din

    2008-11-01

    The structure of the protein–surfactant complex of bovine serum albumin (BSA) and cationic surfactants has been studied by small angle neutron scattering. At low concentrations, the CTAB monomers are observed to bind to the protein leading to an increase in its size. On the other hand at high concentrations, surfactant molecules aggregate along the unfolded polypeptide chain of the protein resulting in the formation of a fractal structure representing a necklace model of micelle-like clusters randomly distributed along the polypeptide chain. The fractal dimension as well as the size and number of micelles attached to the complex have been determined.

  10. Cluster Evaluation of Density Based Subspace Clustering

    OpenAIRE

    Sembiring, Rahmat Widia; Zain, Jasni Mohamad

    2010-01-01

    Clustering real world data often faced with curse of dimensionality, where real world data often consist of many dimensions. Multidimensional data clustering evaluation can be done through a density-based approach. Density approaches based on the paradigm introduced by DBSCAN clustering. In this approach, density of each object neighbours with MinPoints will be calculated. Cluster change will occur in accordance with changes in density of each object neighbours. The neighbours of each object ...

  11. Clustering with Spectral Methods

    OpenAIRE

    Gaertler, Marco

    2002-01-01

    Grouping and sorting are problems with a great tradition in the history of mankind. Clustering and cluster analysis is a small aspect in the wide spectrum. But these topics have applications in most scientific disciplines. Graph clustering is again a little fragment in the clustering area. Nevertheless it has the potential for new pioneering and innovative methods. One such method is the Markov Clustering presented by van Dongen in 'Graph Clustering by Flow Simulation'. We investigated the qu...

  12. Sparse Convex Clustering

    OpenAIRE

    Wang, Binhuan; Zhang, Yilong; Sun, Wei; Fang, Yixin

    2016-01-01

    Convex clustering, a convex relaxation of k-means clustering and hierarchical clustering, has drawn recent attentions since it nicely addresses the instability issue of traditional nonconvex clustering methods. Although its computational and statistical properties have been recently studied, the performance of convex clustering has not yet been investigated in the high-dimensional clustering scenario, where the data contains a large number of features and many of them carry no information abo...

  13. Enhanced photo-catalytic activity of gold ion and gold modified

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The gold ion modified TiO2 was prepared by means of sol- gelwhereas gold deposited TiO2 was prepared by means of photo- reduction. The physical properties were influenced significantly by the presence of gold ion or gold. The enhanced photo-activity of gold modified TiO2 was quantified in terms of methylene blue degradation. The presence of gold ion in TiO2 lattices or gold on TiO2 surface enhanced their photo-activity. The optimum molar content of gold ion doping and gold deposition all was 0.5%. The first-order rates constants of gold modified TiO2 was more than that of pure TiO2, and decreased by increasing the content of gold ion and gold when their contents were more than 0.5%. Gold iondoped in TiO2 lattices was more effective to enhance the photo-activity than gold on TiO2 surface. Moreover, the relationship between physical properties, chemical properties and photo-activityhas been discussed.

  14. Formation of bimetallic nanoalloys by Au coating of size-selected Cu clusters

    International Nuclear Information System (INIS)

    Bimetallic clusters display new characteristics that could not be obtained by varying either the size of pure metallic systems or the composition of bulk bimetals alone. Coating of pre-deposited clusters by vapour deposition is a typical synthesis process of bimetallic clusters. Here, we have demonstrated that hierarchical, gold cluster-decorated copper clusters as well as both heterogeneous and homogeneous Cu–Au bimetallic clusters (4.6 to 10.7 nm) can be prepared by coating pre-deposited, size-selected Cu5000 (4.6 ± 0.2 nm) with Au evaporation at various temperatures. These bimetallic clusters were analyzed by aberration-corrected scanning transmission electron microscopy and associated electron energy loss spectroscopy. The results indicate that the growth of bimetallic clusters is controlled by a competition between nucleation and diffusion of the coating Au atoms.

  15. Template synthesis of braided gold nanowires with gemini surfactant-HAuCl{sub 4} aggregates

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wentao; Han Yuchun; Gao Mingyuan, E-mail: gaomy@iccas.ac.cn; Wang Yilin, E-mail: yilinwang@iccas.ac.cn [Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Key Laboratory of Colloid and Interface Science (China)

    2013-01-15

    One-dimensional braided gold nanowires with 40-50 nm in width and several micrometers in length which were fabricated by using cationic gemini surfactant hexamethylene-1,6-bis (dodecyl dimethylammonium bromide) (C{sub 12}C{sub 6}C{sub 12}Br{sub 2}). Through simply regulating the mole ratio of C{sub 12}C{sub 6}C{sub 12}Br{sub 2} to HAuCl{sub 4}, the morphology of the gold products changed into nanoparticles and nanowires. The CryoTEM images indicated that the C{sub 12}C{sub 6}C{sub 12}Br{sub 2}/HAuCl{sub 4} mixture formed spherical or fibrillar aggregates depending on the mole ratio of C{sub 12}C{sub 6}C{sub 12}Br{sub 2} to HAuCl{sub 4}, which performed as the versatile templates for morphology-controlled synthesis of the multiple gold nanomaterials. The HRTEM and SAED results suggested the nanowires and braided nanowires were polycrystalline. The gold nanostructure displayed a time-dependent growth process, i.e., first the nanoparticles arranged in one dimension, and then assembled into nanowires. Therefore, a template-directed aggregation and fusion process of nanoparticles is proposed for the formation of the one-dimensional gold nanomaterials. The braided nanowires exhibited a higher catalytic activity in the reduction of p-nitroaniline than that of the nanowires. This gemini surfactant-based template provides a versatile strategy for the morphology-controlled synthesis of gold nanomaterials, and may be applied for the synthesis of other noble-metal nanomaterials.

  16. Chemical sensors based on π-conjugated organic molecules and gold nanoparticles

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Scientists have developed techniques for synthesizing and characterizing many new materials including conjugated small molecules, polymers and gold particles protected by conjugated organic chromophores for testing specific sensing properties in the past decade. Still, the design and synthesis or supermolecular systems fabrication of novel materials with controlled sensing properties is a significant and ongoing challenge within nanoscience and nanotechnology. Recently, our group has successfully constructed a series of chemosensors using small organic molecules, conjugated polymers and gold nanoparticles for real-time detection of specific analytes. The chemosensors show high selectivity and sensitivity in the detection of cations and biologic analytes and thus are potentially promising for applications in sensing assay system. In this review, recent sutdies on the design, synthesis and photo-physical properties of novel materials and construct of chemosensors are summarized with an emphasis on the development in our groups in recent years.

  17. Tunnelling conductive hybrid films of gold nanoparticles and cellulose and their applications as electrochemical electrodes.

    Science.gov (United States)

    Liu, Zhiming; Wang, Xuefeng; Li, Mei; Wu, Wenjian

    2015-11-20

    Conductive hybrid films of metal nanoparticles and polymers have practical applications in the fields of sensing, microelectronics and catalysis, etc. Herein, we present the electrochemical availability of tunnelling conductive hybrid films of gold nanoparticles (GNPs) and cellulose.The hybrid films were provided with stable tunnelling conductive properties with 12 nm GNPs of 12.7% (in weight). For the first time, the conductive hybrid films were used as substrates of electrochemical electrodes to load calmodulin (CaM) proteins for sensing of calcium cations.The electrodes of hybrid films with 20 nm GNPs of 46.7% (in weight) exhibited stable electrochemical properties, and showed significant responses to calcium cations with concentrations as low as 10(−9) M after being loaded with CaM proteins. PMID:26511782

  18. Von Gold Plasmonen und Exzitonen : Synthese, Charakterisierung und Applikationen von Gold Nanopartikeln

    OpenAIRE

    Bomm, Jana

    2013-01-01

    In dieser Arbeit wurden sphärische Gold Nanopartikel (NP) mit einem Durchmesser größer ~ 2 nm, Gold Quantenpunkte (QDs) mit einem Durchmesser kleiner ~ 2 nm sowie Gold Nanostäbchen (NRs) unterschiedlicher Länge hergestellt und optisch charakterisiert. Zudem wurden zwei neue Synthesevarianten für die Herstellung thermosensitiver Gold QDs entwickelt werden. Sphärische Gold NP zeigen eine Plasmonenbande bei ~ 520 nm, die auf die kollektive Oszillation von Elektronen zurückzuführen ist. Gold NRs ...

  19. Analysis of gold and silver concentration on gold mining tailings by neutron activation analysis

    International Nuclear Information System (INIS)

    Full text: Instrumental neutron-activation analysis without radiochemical separation is one of most applicable and often used methods to analyze the concentration of gold, silver and other rare and noble metals in gold ores. This method is not suitable for analyzing low concentration of gold and silver in gold mining tailings due to rather high concentration of some elements. Samples are dissolved by boiling in a mixture of concentrated hydrochloric and nitric acids to extract gold and silver into the solution. Chemical yield of gold and silver after dissolution of the sample and further chromatographic separation is between 92 and 95 percent respectively

  20. CMS Industries awarded gold, crystal

    CERN Multimedia

    2006-01-01

    The CMS collaboration honoured 10 of its top suppliers in the seventh annual awards ceremony The representatives of the firms that recieved the CMS Gold and Crystal Awards stand with their awards after the ceremony. The seventh annual CMS Awards ceremony was held on Monday 13 March to recognize the industries that have made substantial contributions to the construction of the collaboration's detector. Nine international firms received Gold Awards, and General Tecnica of Italy received the prestigious Crystal Award. Representatives from the companies attended the ceremony during the plenary session of CMS week. 'The role of CERN, its machines and experiments, beyond particle physics is to push the development of equipment technologies related to high-energy physics,'said CMS Awards Coordinator Domenico Campi. 'All of these industries must go beyond the technologies that are currently available.' Without the involvement of good companies over the years, the construction of the CMS detector wouldn't be possible...